Hazardous substances in Europe`s fresh and marine waters — An

Transcription

EEA Technical report
No 8/2011
Hazardous substances in Europe's fresh and marine waters
An overview
ISSN 1725-2237
EEA Technical report
No 8/2011
Hazardous substances in Europe's fresh and marine waters
An overview
Cover design: EEA
Layout: EEA/Pia Schmidt
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Commission or other institutions of the European Union. Neither the European Environment Agency
nor any person or company acting on behalf of the Agency is responsible for the use that may be
made of the information contained in this report.
Copyright notice
© EEA, Copenhagen, 2011
Reproduction is authorised, provided the source is acknowledged, save where otherwise stated.
Information about the European Union is available on the Internet. It can be accessed through the
Europa server (www.europa.eu).
Luxembourg: Publications Office of the European Union, 2011
ISBN 978-92-9213-214-9
ISSN 1725-2237
doi:10.2800/78305
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Contents
Contents
Acknowledgements..................................................................................................... 4
Executive summary..................................................................................................... 5
1Introduction........................................................................................................... 9
2 Sources, pathways and emissions........................................................................ 11
2.1Introduction.....................................................................................................11
2.2 Urban environment...........................................................................................11
2.3Agriculture.......................................................................................................12
2.4Mining.............................................................................................................12
2.5 Landfills and contaminated land..........................................................................12
2.6 Transport of hazardous substances to coastal waters��13
2.7 Sources emitted directly into the marine environment��13
2.8 Case studies....................................................................................................14
3 Hazardous substances in water, aquatic biota and sediment — current
concentrations and recent trends......................................................................... 22
3.1Introduction.....................................................................................................22
3.2 Chemical status of Europe's water bodies as reported under the WFD......................22
3.3 Pan-European monitoring of organic substances....................................................24
3.4 Transitional, coastal and marine waters................................................................27
4 Impacts of hazardous substances in water........................................................... 31
4.1Introduction.....................................................................................................31
4.2 Impacts on aquatic ecosystems..........................................................................31
4.3 Human health and chemicals in the environment...................................................34
4.4 Human exposure to hazardous substances via water��35
5 Protecting Europe's fresh and marine waters from chemical pollution................. 37
5.1Introduction.....................................................................................................37
5.2REACH ...........................................................................................................39
5.3 Water Framework Directive (WFD) and Environmental Quality Standards
Directive (EQSD)..............................................................................................40
5.4 IPPC and E-PRTR..............................................................................................41
5.5 Sustainable use of pesticides .............................................................................41
5.6 Marine Strategy Framework Directive..................................................................42
5.7 Regional Sea Conventions .................................................................................42
5.8 Substance-specific legislation ............................................................................42
6 Improved assessment and modelling tools........................................................... 44
7Conclusions.......................................................................................................... 47
7.1 Hazardous substances in water affect aquatic life and pose risks to human health 47
7.2 Legislation continues to play an important role, but challenges exist��47
7.3 The potential risks posed by emerging pollutants are insufficiently understood
47
7.4 The ubiquity of some hazardous substances presents particular challenges 47
7.5 The quantitative understanding of sources and emissions must be improved
48
7.6 Smart monitoring and assessment tools are required��48
7.7 Chemicals should be produced and used more sustainably��48
7.8 Climate change will also affect chemical water quality ��49
7.9 Training for expertise in environmental risk assessment should be supported
49
Main abbreviations and acronyms............................................................................. 50
References................................................................................................................ 51
Annex 1 EU projects.................................................................................................. 61
Hazardous substances in Europe's fresh and marine waters — An overview
3
Acknowledgements
Acknowledgements
EEA lead author
EEA
Robert Collins.
Peter Pärt, Dorota Jarosinska, Waldemar Jarosinski,
Trine Christiansen, Bo Jacobsen, Beate Werner,
Paul Csagoly.
Contributing authors
Werner Brack (Helmholtz Centre for Environmental
Research),
Hans‑Christian Holten Lützhøft, Eva Eriksson
(DTU Environment),
Poul Bjerregaard (University of Southern Denmark),
Alistair Boxall (University of York),
Tom Hutchinson (CEFAS),
Nicole Adler, Anette Kuester (UBA),
Thomas Backhaus (University of Gothenburg),
Igor Dubus (Footways),
Lars Otto Reiersen (AMAP).
4
European Commission
DG Environment; Jorge Rodriguez‑Romero,
Helen Clayton,
JRC; Robert Loos, Bernd Gawlik.
EEA's European Topic Centre on Inland, Coastal
and Marine Waters (ETC‑ICM)
Vít Kodeš, Hana Prchalová, Renata Filippi,
Violeta Kuzmickaite, Anita Künitzer (CENIA),
Norman Green, Anders Ruus (NIVA),
Kim Gustavson, Morten Bjergstrøm (DHI).
Executive summary
Executive summary
Chemicals are an essential part of our daily lives.
They are used to produce consumer goods, to
protect or restore our health and to boost food
production, to name but a few examples — and
they are also involved in a growing range of
environmental technologies. Europe's chemical and
associated industries have developed rapidly in
recent decades, making a significant contribution
to Europe's economy and to the global trade in
chemicals.
Whilst synthetic chemicals clearly bring important
benefits to society, some of them are hazardous,
raising concerns for human health and the
environment depending on their pattern of use and
the potential for exposure. Certain types of naturally
occurring chemicals, such as metals, can also be
hazardous. Emissions of hazardous substances to
the environment can occur at every stage of their life
cycle, from production, processing, manufacturing
and use in downstream production sectors or by the
general public to their eventual disposal. Emissions
arise from a wide range of land-based and marine
sources, including agriculture and aquaculture,
industry, oil exploration and mining, transport,
shipping and waste disposal, as well as our own
homes. In addition, concern regarding chemical
contamination arising from the exploitation of shale
gas has grown recently.
Hazardous substances in water affect aquatic life…
Hazardous substances are emitted to water bodies
both directly and indirectly through a range of
diffuse and point source pathways. The presence of
hazardous substances in fresh and marine waters
and associated biota and sediment is documented
by various information sources, including national
monitoring programmes, monitoring initiatives
undertaken by the Joint Research Centre (JRC),
reporting under the Water Framework Directive
(WFD), international marine conventions
(e.g. HELCOM and OSPAR) and European research
studies. These substances comprise a wide range
of industrial and household chemicals, metals,
pesticides and pharmaceuticals.
Hazardous substances can have detrimental
effects on aquatic biota at molecular, cellular,
tissue, organ and ecosystem level. Substances with
endocrine‑disrupting properties, for example, have
been shown to impair reproduction in fish and
shellfish in Europe, raising concerns for fertility and
population survival. The impact of organochlorines
upon sea birds and marine mammals is also
well documented, as is the toxicity of metals and
pesticides to freshwater biota. From a socio‑economic
point of view, such impacts diminish the services
provided by aquatic ecosystems, and consequently
the revenue that can be derived from them.
…and can pose risks to human health
Human exposure to man-made chemicals has been
implicated in a range of chronic diseases, including
cancer as well as reproductive and developmental
impairment. Exposure to toxic chemicals can occur
via inhalation, ingestion and direct contact with skin,
although the understanding of the relative risk posed
by each of these exposure routes remains incomplete.
However, exposure can be linked to the presence of
hazardous substances in water, through the ingestion
of contaminated drinking water and the consumption
of contaminated freshwater fish and seafood.
The exceedance of regulatory levels in seafood is
documented for several hazardous substances in
the seas around Europe. In addition, whilst human
exposure to mercury in the Arctic, in part through
the consumption of marine food, has declined,
concentrations in the blood of more than 75 % of
women sampled in Greenland exceed US guideline
levels.
Alongside concerns about exposure to individual
substances, awareness is growing with regard to
the importance of mixtures of several chemicals, as
found in the more polluted water bodies of Europe.
Laboratory studies have shown that the combined
effects of chemicals upon aquatic life can be additive
— resulting in observable detrimental effects for
combinations of chemicals even if these are present,
individually, at levels below which any adverse
effects can be detected. Such concerns also extend
to potential effects arising from human exposure
to a mixture of chemicals via various pathways,
including water. Biological effects‑directed
measurements have proved to be effective in
addressing the problems of complex chemical
mixtures in European water bodies.
In addition to the potential for adverse impacts
upon human and ecosystem health, the presence of
5
Executive summary
hazardous substances in drinking water supplies
requires their removal. Alternatively, where the
level of treatment involved is so high as to be
uneconomic, a supply can be decommissioned.
In both cases, significant costs are incurred. A key
measure for reducing the level of purification
required for Europe's drinking water is the
establishment of safeguard or protection zones
around the source. The creation of such zones,
recognised in the WFD legislation, must be
associated with regulatory powers to control
polluting activities.
pollutants have been designated as priority
hazardous substances (PHSs) due to their toxicity,
their persistence in the environment and their
bioaccumulation in plant and animal tissues.
The EQSD requires cessation or phase-out of
discharges, emissions and losses of PHSs. For any
substance identified as being of concern at local,
river basin or national level, but not as a PS or PHS
at EU level, standards have to be set at national
level. Compliance with this requirement is critical.
Legislation designed to protect Europe's waters…
Some recent information with respect to the
chemical status of Europe's surface water bodies is
available within the WFD river basin management
plans (RBMPs) which indicate, in general terms,
that a variety of hazardous substances pose a threat
to good chemical status in Europe. These include
certain substances, for example mercury, TBT and
polyaromatic hydrocarbons (PAHs), which can
be described as persistent, bioaccumulative and
toxic and which occur widely in the environment.
Although regulation has led to documented
reductions in the emissions of such substances to
air and water (indeed, the presence of many is a
legacy of past use), their persistence and ubiquity,
particularly in sediment and biota, mean that they
continue to pose a risk to aquatic environments
even at sites far from human activity. The presence
of these substances can cause widespread failure
to achieve good chemical status under the
WFD despite, in some cases, the absence of any
significant risk from other types of substances.
The implementation of more established legislation
related to chemicals has produced positive
outcomes. Abatement measures established under
the Integrated Pollution Prevention and Control
(IPPC) Directive, for example, have contributed
to a decline in metal emissions to water and air,
whilst legislation relating to the production, use
and disposal of polychlorinated biphenyls (PCBs)
has resulted in declines in concentrations found in
marine biota. A similar outcome has resulted from
the banning of tributyltin (TBT) in anti‑fouling
paints due to its endocrine-disrupting impacts
on marine invertebrates, although high levels in
marine sediments can still be observed in certain
locations.
Europe has also introduced a range of relatively
recent legislation to address the use of chemicals and
their emissions to the environment, including water.
The Regulation on the Registration, Evaluation,
Authorisation and Restriction of Chemicals
(REACH), designed to improve the protection of
human health and the environment from the risks
posed by chemicals, has a key role to play in this
respect. REACH attributes greater responsibility
to industry with regard to managing these risks
and providing safety information on substances
used. The Regulation also calls for the progressive
substitution of the most dangerous chemicals once
suitable alternatives have been identified.
The chemical quality of Europe's surface waters
is primarily addressed by the recently adopted
Environmental Quality Standards Directive
(EQSD). This WFD 'daughter' directive defines
concentration limits for pollutants of EU-wide
relevance known as priority substances (PSs).
The limits are defined both in terms of annual
average and maximum allowable concentrations,
with the former protecting against long-term
chronic pollution problems and the latter against
short‑term acute pollution. Some of these
6
…is facing new challenges
Some hazardous substances are hydrophobic and
tend to accumulate in sediment and biota, with the
result that their concentrations in these matrices are
likely to be higher and, therefore, more detectable
and measurable than in water. If measurements
are made in the water column, the risk to the
aquatic environment may be underestimated, and
if different matrices are used in different locations
and across different Member States, the results may
not be directly comparable. A harmonisation at EU
level is, therefore, desirable.
For some pollutants, awareness and a currently
incomplete understanding of potential effects
have developed only recently. These emerging
pollutants include substances that have existed for
some time, such as pharmaceuticals and personal
care products, but also relatively new substances,
such as nanomaterials. Their inclusion in routine
monitoring programmes has so far been limited,
making it difficult to robustly assess the risks to
the environment and human health, and thus to
Executive summary
justify regulation and better monitoring. Targeted
monitoring of selected emerging pollutants
across the EU would be desirable to ensure timely
awareness of potentially problematic substances
that might need to be regulated. This monitoring
should be supported by European research studies.
The question of hazardous substances in Europe's
fresh and marine waters is a complex issue,
and climate change will add a further layer of
complexity. In the absence of appropriately strong
measures, this phenomenon is likely to adversely
affect chemical water quality over the coming
decades. In regions where more intense rainfall is
expected, the frequency and severity of polluted
urban storm flows is predicted to increase, whilst
the flushing to water of agricultural pollutants,
including pesticides and veterinary medicines,
may be exacerbated. Hotter, drier summers and
increasingly severe and frequent droughts will
deplete river flows, reducing contaminant dilution
capacity and leading to elevated concentrations of
hazardous substances. Rising water temperatures
and other stressors associated with climate change
may interact with hazardous substances to impact
the immune system health of aquatic organisms.
Ocean acidification, driven by increasing
atmospheric carbon dioxide (CO2), may change
the speciation of metals in seawater and, therefore,
their interaction with marine organisms. In
addition, coastal erosion — likely to be intensified
by climate change — may lead to the exposure
of historical landfill sites along the coastlines of
Europe, releasing hazardous substances to coastal
waters.
Effective measures exist…
A range of measures can be implemented to reduce
the emission of hazardous substances to water. It
encompasses product substitution, restrictions on
marketing and use, requirements to demonstrate
the implementation of clean production processes
and best available techniques in applications for
industrial permits, fiscal instruments, the setting
of emissions and environmental quality standards,
and action to raise public awareness.
Whilst controls 'at source' are desirable, it is
very likely that other measures to attenuate the
emission of hazardous substances to water will
remain essential. Such measures include advanced
wastewater treatment, urban stormwater controls
and specific agri-environmental practices such
as riparian buffer strips. Reducing emissions of
hazardous substances has been shown to yield
economic and societal benefits.
…but they rely on sound information
It is not practical or affordable to sample and
analyse at sufficient spatial and temporal resolution
for hundreds of individual chemicals within
fresh and marine waters, including aquatic biota
and sediments. However, the focus upon a few
pre‑selected priority substances bears a strong risk
of missing other problematic substances. In addition,
such an approach disregards the effects of chemical
mixtures.
To address these issues, recent European research
studies have led to the development and testing
of new assessment and modelling tools that help
to link chemical contamination with observed
deterioration of ecological quality. Such tools
include approaches to evaluate existing chemical
and biological monitoring data, together with
site-specific experimental techniques to establish
cause-effect relationships. Further development of
biological effects tools integrated with analytical
chemistry is desirable and could contribute, in due
course, to the identification of substances associated
with risks, in the wider context of the update of
the WFD Article 5 'pressures and impacts' analysis.
European research funds can play an important role
in the further development of these tools.
For many hazardous substances, information on
industrial emissions to water must be reported
under the European Pollutant Release and
Transfer Register (E-PRTR). To date, however,
reporting under E-PRTR is incomplete as to the
spatial extent and temporal resolution of data
describing emissions to water — markedly so,
for some substances. It is important not only to
overcome this limitation in the reporting, but also
to improve the quantitative understanding of the
sources, emissions and pathways of all hazardous
substances significantly. Advances in this area
will facilitate the identification of appropriate
measures to address chemical pollution of aquatic
environments.
Chemicals should be produced and used more
sustainably
Despite the comprehensive suite of legislation now
implemented throughout Europe, the ubiquitous
use of chemicals in society and their continuous
release represent a major challenge in terms of
the protection of aquatic ecosystems and human
health. Efforts to promote a more sustainable
consumption and production of chemicals are
needed. They are likely to require a mix of
policy responses, including regulation, economic
7
Executive summary
incentives and information-based instruments.
Implementing a more sustainable approach to the
consumption and production of chemicals would
not only benefit Europe's environment but also
reduce the detrimental effects arising in other parts
of the world as a result of the growing proportion of
goods imported to Europe.
To help achieve a more sustainable production
of chemicals, wider implementation of 'green
8
chemistry' is required. This approach involves
developing new processes and technologies that
maintain the quality of a product but reduce or
eliminate the use and generation of hazardous
substances. The adoption of sustainable, green
chemistry techniques has been shown to generate
financial benefits and hence provide competitive
advantage. Currently, however, there is no
comprehensive EU legislation on sustainable
chemistry in place.
Introduction
1Introduction
Chemical substances are an essential part of our
daily lives. They are used in health and consumer
products, in food production and in a growing
range of environmental technologies, to name but
a few examples. They can be natural substances,
they can be formed as the unintended by-product
of natural and human-induced processes, or they
can be synthesised specifically for use in industrial
processes and consumer products (OSPAR, 2009a).
Tens of thousands of chemicals are available on
the European market, with the European Union
holding a substantial share of global exports and
imports.
Union amounted to approximately 200 million
tonnes in 2008 (Figure 1.1). Following several
decades of substantial growth, it has tended to
stabilise in recent years.
Whilst chemicals bring important benefits to society,
some of them are hazardous, raising concerns for
human health and the environment depending on
their pattern of use and environmental exposures.
Annual production of hazardous chemicals (i.e. toxic
chemicals as defined by Eurostat) in the European
Figure 1.1
Hazardous substances are released to the wider
environment via various pathways, with the
potential for detrimental effects upon both terrestrial
and aquatic ecosystems. Observations from aquatic
ecosystems in the 1950s and 1960s were the first
early warnings of the environmental dangers of the
widespread production and use of industrial and
man-made chemicals, including persistent organic
pollutants (POPs). The concern that arose led to
the implementation (in 1976) of the Dangerous
Substances Directive (now integrated into the WFD)
which aimed to eliminate pollution by a select list
of substances and reduce the level of certain others.
This directive, coupled with other international
initiatives, led to the decline of certain substances,
Production of toxic chemicals in the EU
Production volumes of toxic chemicals in EU (27 countries)
106 tonnes
250
200
150
100
50
0
2002
Note:
2003
2004
2005
2006
Carcinogenic, mutagenic, reprotoxic chemicals
Chronic toxic chemicals
Toxic chemicals
Harmful chemicals
2007
2008
Very toxic chemicals
The graph was compiled for 168 toxic chemicals based on production quantities collected pursuant to the Prodcom regulation
(Council Regulation (EEC) 3924/91 on the establishment of a Community survey of industrial production). The toxicity
classes were assigned according to the classification and labelling system ('risk phrases' or R-phrases) designated for the
individual substances in Annex VI to the Dangerous Substances Directive as amended by EC Directive 2001/59/EC (adapting
to technical progress for the 28th time Council Directive 67/548/EEC on the approximation of the laws, regulations and
administrative provisions relating to the classification, packaging and labelling of dangerous substances).
Source: Eurostat.
9
Introduction
including some metals and POPs, in aquatic
environments (EEA, 2003).
In recent years, the body of information, derived
from numerous sources, describing the presence of
hazardous substances in Europe's fresh, estuarine,
coastal and marine waters has grown. In addition
to those substances of early concern, such as POPs,
certain metals and pesticides, the presence of
pharmaceuticals, personal care products, phenols
and phthalates is documented. In some locations,
these various substances are known to occur at a
level sufficient to cause detrimental impacts upon
aquatic biota. Such toxic impacts diminish the highly
valuable services that can be derived from marine
and freshwater ecosystems (Martinez et al., 2007).
Aside from the effects upon aquatic biota, water
is also a pathway by which humans can become
exposed to hazardous substances — via drinking
water supplies that have been inadequately treated,
or through the consumption of contaminated
freshwater fish and sea food.
A range of legislation and policy is now in force
to address the use of hazardous substances,
their release to Europe's environment, including
its waters, and their levels within aquatic
environments. Much of this legislation has been
implemented relatively recently, including REACH
and the WFD, although some, such as the IPPC
Directive and its regulation of industrial emissions,
is more established.
In addition to the significant legislative
developments of recent years, a rapidly expanding
body of information is available with respect to the
presence and toxic impacts of hazardous substances
in Europe's fresh and marine waters. Typically,
however, this information is fragmented in nature,
and any individual sources of information tend to
focus on specific aspects, for example, a particular
geographical region, a distinct chemical group, or
a single organism of concern. The objective of this
report, therefore, is to address this limitation and
provide a broad, integrated and up-to-date overview
of the issue of hazardous substances in Europe's
water. More specifically, this report aims to:
• document the sources, pathways, emissions and
discharges of selected hazardous substances to
Europe's fresh and marine waters (Chapter 2);
10
• provide an overview of the current status of, and
recent trends in, chemical pollution of Europe's
fresh and marine waters using information from
a variety of sources, including reporting under
the WFD, the EEA's Eionet-Water database and
monitoring programmes conducted by the JRC
and regional sea conventions (Chapter 3);
• describe some of the impacts that hazardous
substances can have upon aquatic biota and
outline the potential for human exposure to these
substances via water (Chapter 4);
• outline key European policy and legislation that
addresses the use of hazardous substances and
their release to water (Chapter 5);
• highlight selected measures to reduce the
emissions of hazardous substances to water
(Chapter 5);
• present tools and innovative approaches to assess
the sources, levels and effects of hazardous
substances, including chemical mixtures
(Chapter 6);
• provide a supporting background document
for the various chemicals-related parts of the
EEA's forthcoming 2012 'State of Europe's water'
reporting, to be undertaken in conjunction with
the European Commission.
The term 'hazardous substances' is, by necessity,
used in a broad sense throughout this report,
encompassing substances of very high concern
as defined by REACH, hazardous substances as
defined by OSPAR, the PSs, PHSs and Annex VIII
pollutants identified by the WFD, and a number
of the substances subject to E-PRTR reporting. In
addition, the use of the term includes the potentially
wide-ranging list of substances for which Member
States are to establish their own surface and
groundwater standards. It is important to note that
designation and classification under this suite of
legislation is ongoing, as are the authorisation of
substances under REACH and the designation of PS
under the EQSD. The report also refers to 'emerging
pollutants', i.e. those for which the potential for
adverse effects has only recently become apparent
and for which the understanding of such effects is
currently incomplete.
Sources, pathways and emissions
2 Sources, pathways and emissions
2.1Introduction
Emissions and releases of hazardous substances
can occur at all stages of their life-cycle, from
production, processing, manufacturing and use
in downstream production sectors and by the
general public to the eventual disposal of these
substances. This chapter provides an overview of
the key sources of hazardous substances and of the
pathways by which these substances are emitted to
both fresh and marine waters.
In addition, a series of case studies examines
five selected hazardous substances (or groups of
substances) to illustrate the diversity of patterns of
emissions, pathways and environmental fate. These
include metals for which environmental toxicity
has long been understood, emerging pollutants
for which the potential for detrimental effects has
only recently become apparent, and ubiquitous
substances that are transported over long distances
in the atmosphere. Another subsection focuses on
a heterogeneous group of substances that cause a
particular detrimental effect in aquatic biota — the
phenomenon of endocrine disruption.
2.2 Urban environment
Hazardous substances arise from various sources
in the urban environment. These include household
chemicals such as personal care products and
medicines, a wide range of industrial chemicals,
substances such as hydrocarbons and heavy
metals released by the transport sector, building
and construction materials, and pesticides used to
control unwanted plant growth on sports grounds
and buildings, in public parks and private gardens,
and on roads and railways.
Certain hazardous substances are released to air
from industrial and waste facilities and vehicle
emissions. Subsequently, their deposition to water
bodies can occur both directly and indirectly, for
example via soil and urban drainage systems.
In some cases deposition may occur close to the
point of emission, although some hazardous
substances, such as mercury and persistent organic
pollutants, are known to be subject to long‑range
transboundary atmospheric transport. As a
consequence, they can adversely affect aquatic
environments in remote regions such as the Arctic.
Addressing their impacts requires political initiative
at the regional and the global scale.
Household wastewater in Europe is predominantly
collected by a sewer network and directed to
municipal wastewater treatment plants. Industrial
wastewaters are also typically treated, either on-site
or by transfer to a municipal plant. Other urban
pollutants, however, particularly those deposited
from the atmosphere or released from vehicles
(e.g. from wear on brakes and tyres) are, originally
at least, diffuse in nature, as they are washed
from impervious areas by surface run-off. Their
subsequent fate depends upon whether the run‑off
is collected and directed to a treatment plant or
discharged untreated to a receiving water body.
Whilst household and industrial wastewater
treatment has been implemented progressively
across Europe, the process does not remove
all hazardous substances, with household and
industrial chemicals and pharmaceuticals, for
example, being detected in treated effluent that is
subsequently discharged to surface waters (Ashton
et al., 2004; Gros et al., 2010; HELCOM, 2010; Miège
et al., 2009; Reemtsma et al., 2006). Such discharges
are near-continuous and hence these substances do
not need to be persistent in nature to give rise to
chronic effects in aquatic ecosystems. In addition,
sewage sludge generated via municipal wastewater
treatment can be contaminated by hazardous
substances including pharmaceuticals (Giger et al.,
2003) and personal care products (Brausch and
Rand, 2011).
In many cities across Europe, the sewage collection
system has also been designed to collect run-off
from streets, roofs and other impervious surfaces.
The collection pipes and treatment plants of such
combined systems are designed to be able to handle
both sewage and urban run-off generated during
rain storms, but only up to a certain level. During
larger storm events, the combined flow generated
can exceed the capacity of the system. When this
happens, relief structures are built into the collection
system to prevent sewage back-up into streets and
homes, enabling the flows to bypass the treatment
plants and discharge the combined waste more
or less untreated to a receiving watercourse. Such
combined sewer overflows (CSOs), together with
11
discharges from separate stormwater systems,
typically discharge a range of pollutants including
hazardous substances (Chon et al., 2010; Gounou
et al., 2011; Sally et al., 2011) and can cause rapid
depletion of oxygen levels in receiving waters (Even
et al., 2007). In addition, the quality of coastal waters
near such discharges can deteriorate very quickly.
However, other than in respect of their design
criteria, neither CSOs nor discharges from
separate stormwater systems are subject to direct
environmental regulation, and little information is
publicly available describing their pollutant loads.
Innovative solutions are required, particularly as the
retro-separation of combined sewers is expensive
and technically challenging. Good practice is
already apparent in Europe in this respect, such as
the retention of overflows in storage ponds during
heavy rainfall, with a subsequent back-pumping to
the system for treatment. In the Greater Paris region,
for example, such stormwater retention ponds have
contributed to a clear decline in sewer overflow
volumes (Meybeck et al., 2007).
2.3Agriculture
Pesticides used in agriculture are widely detected in
freshwater, often transported by diffuse pathways
via surface run-off and leaching. Point discharges of
pesticides are also important, however, and occur
through accidental spillage, sprayer loading and
wash-down, and inappropriate storage and disposal.
Just how much pesticide pollution of freshwater
occurs depends on a range of factors including
the chemical nature of the pesticide, the physical
properties of the landscape, and weather conditions.
Biocidal products are also used, for example to treat
livestock and protect stores. Wash-off and accidental
spillage may occur.
Metal emissions from agriculture include cadmium,
found naturally in the phosphate rock used to make
fertiliser, and zinc, an essential trace element that
is added to animal feed. A significant proportion of
zinc is not absorbed by livestock, however, and is
excreted in manure that may then be flushed into
rural streams. Copper, too, is found in feedstuffs and
hence manure, but can also come from copper baths
used in the treatment and disinfection of livestock
hooves. While metals are generally well retained in
soil, there is evidence that agricultural sources can
make a significant contribution to freshwater loads
(RIVM, 2008a and 2008b).
Veterinary medicinal products are found in manure
and slurry, excreted directly by grazing livestock or
spread on to land after a period of storage. Once on
the land surface, they are susceptible to run-off into
surface waters or infiltration to groundwaters.
2.4Mining
Mining exerts a localised but significant pressure
upon the chemical and ecological quality of water
resources in parts of Europe, particularly with
respect to the discharge of heavy metals. Abandoned
mines represent a particular threat since, in the
absence of continued pumping, groundwater levels
rise and, ultimately, discharge contaminants within
the mine workings. Mine discharges threaten the
attainment of good water quality in a number of
locations across Europe.
2.5 Landfills and contaminated land
Landfill sites can be a source of pollution to the
aquatic environment. Precipitation percolates down
through the waste, picking up a range of pollutants
Box 2.1 Exploitation of shale gas
Concern with respect to chemical contamination associated with the exploitation of shale gas has
recently gained in prominence throughout Europe. With conventional natural gas reserves declining
globally, shale gas has emerged as a potentially significant new source of unconventional gas.
Exploitation of shale gas has been advanced by developments in horizontal drilling and well stimulation
technologies such as hydraulic fracturing (Wood et al., 2011). The exploitation process does, however,
involve a strong risk of negative environmental impacts, including potential contamination of ground
and surface water by chemicals used in the fracturing process and the mobilisation of sub-surface
contaminants such as heavy metals and naturally occurring radioactive materials (Wood et al., 2011).
In addition, methane contamination of drinking water has been associated with the process (Osborn
et al., 2011). The information required to fully evaluate these risks is currently unavailable. Therefore,
a precautionary approach should be adopted with respect to extraction in Europe.
12
including hazardous substances, whilst water is also
released from the waste itself as it degrades (Slack
et al., 2005). The leachate subsequently collects at
the base of the landfill where it can, potentially,
contaminate groundwater.
(HELCOM, 2010). Re-suspension of hazardous
substances in estuarine and coastal waters can then
occur when sediments are disturbed and displaced,
for example, through dredging (OSPAR, 2009a).
In modern landfills, leachate is collected by pipes and
either treated on site, with the effluent discharged
to a neighbouring watercourse, or transported to
a sewage treatment plant for processing. Older
landfills, however, do not incorporate such leachate
collection or the use of an impermeable base liner.
As a consequence, contaminated leachate is free to
flow downwards unrestricted (Baun et al., 2004). In
the European Union, the Landfill Directive specifies
technical and engineering requirements for water
control and leachate management. In addition,
restrictions on hazardous waste apply.
2.7 Sources emitted directly into the
marine environment
Aside from landfill sites, land can be contaminated
by a range of hazardous substances released from
historical industrial activities or, more recently,
from unintentional leaks and spills. Such substances
can include solvents, oil, petrol, heavy metals and
radioactive substances. Without appropriate remedial
action, ground and surface waters can also be
polluted.
2.6
Transport of hazardous substances
to coastal waters
Once released to rivers, hazardous substances can be
transported downstream and ultimately discharged
to coastal waters, although numerous processes
can occur 'in-stream' to attenuate this transport.
Of particular note is the deposition of substances
onto the river bed. Hazardous substances attached to
other particles, such as organic material and eroded
soil, are particularly susceptible to this sedimentation
process and, once settled on the river bed, can pose a
threat to benthic biota. During periods of higher river
flow, however, bed sediments and their associated
contaminants can be re-suspended into the water
column and transported downstream until flow
declines and sedimentation occurs once more.
This cycle of sedimentation and re-suspension
means that, for a number of hazardous substances,
the total load transported by the river can be
markedly underestimated unless monitoring occurs
during periods of high river flow. The proportion
of a hazardous substance load that is ultimately
discharged to coastal waters remains susceptible
to sedimentation in estuarine and near coastal
waters. Elevated levels of cadmium and mercury,
for example, are observed in Baltic Sea sediments
In addition to the waterborne transport of
substances emitted from land-based sources
and deposition from the atmosphere, hazardous
substances are also released directly into the
marine environment. Shipping, harbour and port
activities, offshore oil exploration and aquaculture
all emit a variety of hazardous substances, whilst
the discharge of sewage and industrial wastewater
directly (i.e. not via rivers) into coastal waters can
also occur.
Pollution from shipping, including oil and other
hazardous substances, arises from accidents as well
as operational and illegal discharges. Some evidence
of decreasing oil pollution is apparent in the OSPAR
region and can be attributed to the capture of
technological advances (such as the phasing out of
single-hull tankers) within international shipping
regulations (OSPAR, 2009b).
Discharges of oil from offshore installations can
occur from produced water, displacement water
and accidental spillage, with flaring operations also
playing a minor role. Produced and displacement
water account for the largest amounts of oil
discharged, with the exception of large, infrequent
oil spills. Both have declined over recent years in the
OSPAR region, a development which is attributable
to the implementation of standards set with respect
to discharge concentrations (OSPAR, 2009c).
In response to increased demand for fish products
and the reduced supply of wild caught fish, a large
increase in total European aquaculture production
has been observed over the past 15 years (FAO,
2010). Today, EU and EFTA aquaculture produces
about 1.8 million tonnes of fish, shellfish and
crustaceans annually, generating a turnover of
around EUR 3.2 billion while supporting 65 000 jobs
(EEA, 2010a). Release to the marine environment of
biocides, antibiotics and anti‑fouling chemicals arises
from the sector, particularly in connection with finfish
production, although any related impacts are thought
to be local and site-specific (OSPAR, 2009d). In recent
years, the increased use of vaccines has reduced
the use of antibiotics in the sector, whilst copper
and (to a lesser extent) zinc have replaced TBT as
anti‑fouling agents.
13
available than inorganic mercury. In the human
body, it has a tendency to accumulate in the nerve
tissue.
2.8 Case studies
2.8.1Mercury
Mercury and most of its compounds are extremely
toxic to both humans (Grandjean et al., 2007) and the
environment and, as a consequence, are classified
as PHSs under the EQSD. Mercury is a persistent
pollutant and subject to long-range transboundary
transport that has contributed to the building of a
global pool of mercury in the environment; about
40 % of annual mercury deposition to Europe
originates from outside the continent (Travnikov,
2005).
Whilst concentrations of mercury in ambient air
are generally too low to present a risk to human
health (UNEP, 2008), concern over mercury in
the atmosphere relates to the fact that, following
deposition, it can be taken up by biota and
subsequently enter the food chain; ingestion via
seafood is a particular concern. The uptake in biota
is facilitated by the conversion of inorganic mercury
to organic methyl mercury. Methyl mercury is
lipid soluble and 10 to 100 times more biologically
Map 2.1
-30°
Methylation in the environment is effected by
bacteria and other microorganisms in the soil
and in lake and coastal sediments. Through this
mechanism, historical deposition of mercury
continues to affect biota. This explains why there
is no obvious reduction in methyl mercury levels
in lake fish in some areas of Europe (Scandinavia).
Recent findings show that atmospheric mercury
deposition to the sea is methylated by algae or
bacteria in the surface film of the water. This is a
likely reason for the surprisingly high concentrations
of methyl mercury found in long-lived fish like tuna,
swordfish and sharks.
In Europe, all mining of mercury has now ceased
and the majority of production results from the
recycling of products and wastes containing
mercury. Mercury is used in the chloro-alkali
industry, in electrical control and switching
devices, measuring and control instruments,
lighting, batteries and dental amalgams. Emissions
Total (dry and wet) deposition of mercury across Europe, in 2008 (g/km2/year)
-20°
-10°
0°
10°
20°
30°
40°
50°
60°
70°
Total (dry and wet)
deposition of Mercury
2008
g/km2/year
<5
5–7
60°
7–10
10–15
50°
15–20
20–30
> 30
50°
40°
40°
0
500
0°
1000
1500 km
10°
20°
30°
40°
Source: European Monitoring and Evaluation Programme (EMEP).
14
of mercury to air in Europe arise predominantly
from combustion facilities and from the metal and
chemical industries.
According to reporting under E-PRTR, European
emissions of mercury to air totalled 37.8 tonnes
in 2008. The implementation of abatement
technologies together with a general decline in
the burning of coal (which contains mercury as a
contaminant) have led to a decrease in emissions to
air of 61 % across EEA member countries between
1990 and 2008. However, unless the abatement
technologies now generally employed in Europe
and North America are implemented in other parts
of the world, global emissions (the largest share
of which originates from the combustion of fossil
Map 2.2
-30°
fuels) are predicted to increase by about 25 % by
2020 (Sundseth et al., 2010). Total deposition (wet
and dry) of mercury currently varies widely across
Europe, from less than 5 g/km2/year to more than
30 g/km2/year (Map 2.1).
Mercury emissions to water reported under E-PRTR
totalled 6.6 tonnes in 2008 (Map 2.2), 'released' from
420 facilities. Much of this total (63 %) was released
from urban wastewater treatment plants, whilst
16 % arose from chemical industrial facilities with
on-site treatment.
However, Map 2.2 should not be viewed as
representing total mercury emissions to water. Three
other factors must be taken into account:
Emissions of mercury to water based on E-PRTR reporting of 2008 data
-20°
-10°
0°
10°
20°
30°
40°
50°
60°
Emission of mercury
(Hg), 2008
Emission of Hg for facility
(kg/year)
60°
< 25
25–100
60°
> 100
Emission of Hg per river
basin district
(g/km2/year)
< 0.5
0.5–5
>5
50°
50°
Outside E-PRTR
region
No emission
reported above
the threshold
40°
40°
0
Note: 500
0°
1000
1500 km
10°
20°
30°
Reported emissions (releases) relate to the following E-PRTR sectors: animal and vegetable products from the food and
beverage sector; chemical industry; energy; mineral industry; paper and wood production and processing; production and
processing of metals; waste and water management; other activities.
Source: Version 2 published on 31 March 2010 (http://www.eea.europa.eu/data-and-maps/data/member-states-reporting-art-7under-the-european-pollutant-release-and-transfer-register-e-prtr-regulation-3).
15
1) Facilities smaller than the E-PRTR thresholds
(and not, therefore, required to report under the
regulation) including many urban wastewater
treatment plants, may contribute significant
emissions of mercury to water.
2) Diffuse sources, which are also not reported
under E-PRTR, may be of significance.
3) Reporting under E-PRTR for mercury may well
be incomplete.
The EU's mercury strategy is a comprehensive
plan addressing mercury pollution both in the EU
and globally. It has resulted in restrictions on the
sale of measuring devices containing mercury, a
ban on exports of mercury from the EU and rules
on safe storage of mercury decommissioned by
industry. The strategy contains 20 measures to
reduce mercury emissions, cut supply and demand
and avoid human exposure, especially to methyl
mercury found in fish. A range of regulations and
directives related to the strategy also plays a key
role, addressing the use of mercury, emissions to
air, and waste disposal.
Map 2.3
-30°
Industry initiatives, in part driven by the IPPC
Directive, are also important. For example, mercury
cells are gradually being replaced by diaphragm and
membrane cells in the chloro-alkali industry. As a
result, mercury emissions from this industrial sector
have fallen from 2.59 to 0.93 g per tonne of chlorine
capacity between 1995 and 2009. Members of Euro
Chlor — the association of chloro-alkali process plant
operators in Europe — have voluntarily agreed to
phase out the remaining use of mercury technology
by the end of 2020 (Euro Chlor, 2010).
The United Nations Environment Programme
(UNEP) has initiated a drive for a globally binding
instrument to control and reduce mercury emissions
(UNEP, 2008) and such reductions have been
shown to yield large economic and societal benefits
(Sundseth et al., 2010).
2.8.2Cadmium
Due to its environmental toxicity and threat to
human health, cadmium, a metal, is classified as a
PHS under the EQSD, which therefore requires that
all discharges, emissions and losses cease over time.
Total (dry and wet) deposition of cadmium across Europe in 2008 (g/km2/year)
-20°
-10°
0°
10°
20°
30°
40°
50°
60°
70°
Total (dry and wet)
deposition of cadmium
2008
g/km2/year
<1
1–5
60°
5–10
10–20
50°
20–50
50–100
> 100
50°
40°
40°
0
500
0°
1000
1500 km
10°
20°
30°
40°
Source: European Monitoring and Evaluation Programme (EMEP).
16
Cadmium is primarily produced as a by-product
from the extraction, smelting and refining of zinc
and other non-ferrous metals. It has predominantly
been used in rechargeable nickel-cadmium batteries,
although sales to consumers have now been banned
in Europe, with the exception of certain uses.
Cadmium is also used in the production of pigments,
coatings and platings.
Emissions of cadmium to air arise primarily from
combustion processes in power plants and industry.
Emissions to water arise from the chemicals and
metals industries, the transport sector and waste
streams, although other sectors, including agriculture,
can also be involved. Agricultural sources of
cadmium derive from the phosphate rock used to
manufacture fertiliser. It is also found in animal feeds
Map 2.4
-30°
and hence in cattle fodder and manure. Whilst metals
are generally well retained in soil, studies in the
Netherlands indicate that about 25 % of the cadmium
load to Dutch surface waters derives from agriculture
(RIVM, 2008a).
Cadmium emissions to air are ultimately deposited
onto land or directly into fresh and marine waters.
Atmospheric deposition in urban areas will
typically result in cadmium being washed from
impervious surfaces, collected and discharged to a
receiving water, either directly or via a wastewater
treatment plant. Combined wet and dry deposition
of cadmium across Europe is variable, generally
ranging between 10 and 50 g/km2/year but reaching
in excess of 100 g/km2/year in parts of central and
south-eastern Europe (Map 2.3). Across the 32 EEA
Emissions of cadmium to water based on E-PRTR reporting of 2008 data
-20°
-10°
0°
10°
20°
30°
40°
50°
60°
Emission of cadmium
(Cd), 2008
Emission of Cd for facility
(kg/year)
60°
< 25
25–100
> 100
60°
Emission of Cd per river
basin district
(g/km2/year)
<1
1–5
>5
50°
Outside E-PRTR
region
No emission
reported above
the threshold
50°
40°
40°
0
Note: 500
0°
1000
1500 km
10°
20°
30°
17
member countries, emissions of cadmium to air
have declined significantly over recent years — by
about 58 % between 1990 and 2008. This decline
reflects improvements in abatement technologies
at industrial facilities and, in some countries, the
closure of older plants as a result of economic
restructuring.
2.8.3 Benzo[a]pyrene
Cadmium in industrial wastewater will, typically,
be directed to a treatment plant, either on site
or at a municipal facility. In the latter case, it is
frequently combined, prior to treatment, with
cadmium washed from urban land. A proportion of
the metal in the wastewater will then be discharged
to a receiving water within treated effluent.
Typically, however, the relative contribution of the
various original sources of cadmium emitted to
municipal wastewater treatment plants is not well
quantified. Map 2.4 illustrates cadmium emissions
to water across Europe, arising predominantly
from industrial facilities and urban wastewater
treatment plants, as reported under E-PRTR. In 2008,
333 facilities and plants across Europe reported
a total combined cadmium emission to water of
21.6 tonnes. As with mercury, however, the E-PRTR
data for cadmium cannot be viewed as reflecting
total emissions to water, as smaller facilities and
diffuse sources are not taken into account, and the
reporting may be incomplete. Emissions of cadmium
to air, as reported under E-PRTR, totalled about
19 tonnes in 2008.
Figure 2.1 Benzo[a]pyrene (B[a]P) is a PAH classified as a PHS
under the EQSD. Achieving the required cessation
in emissions to water will be challenging, however,
given that it reaches surface waters primarily
through atmospheric deposition and, like other
PAHs, can be found in remote areas away from
human activity. B[a]P results from incomplete
combustion processes, such as those related to the
production of electricity, the transport sector, various
industrial sectors and waste incineration.
Substance flow analysis (SFA) undertaken
within the 'Source control options for reducing
emissions of priority pollutants' (ScorePP) project
has produced estimates of B[a]P emissions in a
semi-hypothetical case city (SHCC) typical for
the eastern part of Europe, with a population of
1.2 million (see Chapter 5 for a description of the
approach). The results confirm the dominance of
the release to air (Figure 2.1) with the potential
for significant indirect emissions to surface water
following subsequent atmospheric deposition.
Emission reduction measures with respect to
B[a]P primarily need to focus upon combustion
processes, including those related to the transport
sector as well as coal- and wood-powered heating
and electricity-generating plants.
Estimated emissions (kg/year) of B[a]P, broken down by compartment within a
semi‑hypothetical case city
Emissions, kg/year
Emissions, %
100
5 000
4 000
75
3 000
50
50
40
0.75
30
0.50
20
0.25
10
0
0.00
Stormwater
CSO
WWTP
Urban
surfaces
Surface
water
Air
Sludge
Infiltration
Degradation
Note:'Surface water' corresponds to the sum of emissions within the 'Stormwater', 'CSO', 'WWTP' and 'Urban surfaces'
compartments. 'Air' reflects emissions directly to air. 'Sludge' represents B[a]P within sludge generated by the wastewater
treatment plant (WWTP) and CSO treatment. The 'Infiltration' compartment refers to stormwater sediment and infiltration to
groundwater.
Source: ScorePP.
18
2.8.4 Human and veterinary medicines
(pharmaceuticals)
The occurrence and impacts of pharmaceutical
products in the environment is an emerging
concern that encompasses a range of
human and veterinary medicines, including
antibiotics, anti‑depressives, anti‑epileptics,
anti‑inflammatories, beta-blockers and
parasiticides. Whilst production and consumption
data are limited across Europe, in Germany
alone, more than 9 000 pharmaceuticals with
3 000 different active compounds are registered
for human use, with an annual consumption of
approximately 31 000 tonnes (BPI et al., 2006).
The release of human medicines to freshwater
occurs through various routes. After
administration, they are absorbed, metabolised
and then excreted to a sewer system — often
only slightly transformed or even unchanged.
In addition, despite take-back schemes, unused
medicines are often disposed of improperly via
the sink or toilet. Typically incomplete removal
techniques at urban wastewater treatment plants
(Heberer, 2002; Miège et al., 2009; Reemtsma
et al., 2006) mean that drug residues or their
transformation products are found in treated
effluent discharged to receiving waters (e.g. Ashton
et al., 2004; Gros et al., 2010) and, as a consequence,
in the receiving waters themselves. Human
medicines have also been detected in groundwater,
including drinking water sources, where bank
filtration or artificial groundwater recharge has
occurred downstream from municipal sewage
treatment works (Heberer, 2002). The presence of
pharmaceuticals in groundwater can also derive
from other sources, such as sewer leakage (Ellis,
2006) and landfill leachates (as a result of disposal
via domestic waste) (Ahel and Jelicic, 2001).
Following use in livestock treatment, veterinary
drugs and any metabolites may be released to
soil directly, by animals at pasture, or indirectly,
through the application of animal manures and
slurries to land as a fertiliser (Boxall et al., 2003
and 2004). Veterinary medicines that are released
to soil may subsequently be transported to surface
waters via run-off or field drains (Burkhard et al.,
2005; Kay et al., 2005) or leach to groundwaters
(Blackwell et al., 2007). Another important route
of input of livestock medicines to water bodies is
wash-off from impervious farmyard surfaces. In
aquaculture treatments, the drug is often added
directly to the aquatic environment. Limited
amounts of compounds may also be released to
the environment from the treatment of companion
animals or the improper disposal of unused
products (Boxall et al., 2004). The potential
for a veterinary medicine to be released to the
aquatic environment depends on various aspects,
such as the method of treatment, agriculture or
aquaculture practices, environmental conditions
and the properties of the medicine (Metcalfe et al.,
2008).
2.8.5DEHP
Di(2-ethylhexyl)phthalate (DEHP) is an organic
compound classified as a PS under the WFD, as
a substance of very high concern under REACH
and as a reprotoxic (category 1B) substance under
Regulation (EC) 1272/2008 on the classification,
labelling and packaging of substances and
mixtures. DEHP is used as a plasticiser in polymer
products (mainly in flexible PVC) including pipes
and tubes, flooring and wall lining, sealants,
food packaging, cables and wire sheathing,
underseal for cars, guttering, tarpaulins, clothing
and footwear, toys, office supplies and medical
products such as blood bags and catheters. The
content of DEHP in polymer products varies but
typically approximates 30 %, although it migrates
slowly from such products over their lifetime.
A proportion of the DEHP released to the aquatic
environment stems from discharge of effluent
from municipal sewage treatment plants, deriving
originally from the wide use of PVC in residential,
commercial, medical and industrial premises and
their direct connection to a sewer system. DEHP
is also released into urban run-off. In this case, it
originates from building materials and vehicles
and is subsequently discharged to a water body
directly or indirectly, via a municipal treatment
plant. Stormwater overflows are also a significant
emission pathway (OSPAR, 2006).
DEHP has low water solubility, and leaching
from plastics in landfills is, therefore, relatively
slow. Its low volatility means that emissions of
DEHP to air from PVC materials are low, although
loss to air does occur during waste incineration.
Data reported to E-PRTR (Map 2.5) show that
17.9 tonnes of DEHP were emitted to water from
180 facilities in 2008, 97 % of which was emitted via
143 urban wastewater treatment plants. However,
given its widespread use and the high likelihood
of DEHP discharges from all large municipal
wastewater treatment plants, Map 2.5 suggests that
reporting under E-PRTR is incomplete. Estimates
from other sources indicate that diffuse emissions
— not reported under E-PRTR — are also a
significant source of DEHP (OSPAR, 2006).
19
Map 2.5 Emissions of DEHP to water based on E-PRTR reporting of 2008 data
-30°
-20°
-10°
0°
10°
20°
30°
40°
50°
60°
60°
Emission of
Bis(2-ethylhexyl)phthalate (DEHP), 2008
Emission of DEHP for facility
(kg/year)
< 25
25–100
60°
> 100
Emission of DEHP per river
basin district
(g/km2/year)
< 0.5
0.5–5
50°
>5
Outside E-PRTR
region
50°
No emission
reported above
the threshold
40°
40°
0
Note: 500
0°
1000
1500 km
10°
20°
30°
2.8.6 Endocrine-disrupting chemicals
Concerns have existed for a number of years
about the potential for a heterogeneous group of
substances in the environment to interfere with the
normal functioning of endocrine systems, affecting
reproduction and development in both humans
and wildlife. Such endocrine-disrupting chemicals
(EDCs) have been defined as 'exogenous substances
that alter function(s) of the endocrine system and
consequently cause adverse health effects in an
intact organism, or its progeny, or (sub)populations'
(WHO/IPCS, 2002).
A large range of naturally occurring and man-made
substances have been shown to have potentially
endocrine-disrupting properties. These include
20
pesticides, fungicides, insecticides, industrial
chemicals like PCBs, PAHs, alkylphenols, phthalates
and dioxins, chemicals in personal care products
(e.g. triclosan, an antimicrobial in hand soaps),
and synthetic oestrogens in pharmaceutical
products such as oral contraceptives and hormone
replacement therapy drugs.
Discharges of municipal and industrial wastewater
are a major route of EDCs entering the aquatic
environment. Treatment can remove much of the
influent load (e.g. Andersen et al., 2003; Baronti
et al., 2000; Johnson and Williams, 2004), resulting
in low concentrations (typically parts per trillion)
being discharged within effluent to receiving waters.
However, such low concentrations, especially of
highly biologically active steroid hormones, can
still result in endocrine disruption in aquatic biota
(Jobling et al., 2006).
The occurrence of endocrine disruption in
freshwater fish in areas not directly affected
by discharges from sewage treatment plants
indicates that other sources exist (Bjerregaard
et al., 2008). Livestock, for example, are also a
source of oestrogenic hormones, and studies in
surface waters draining intensive livestock farms
suggest that levels may be high enough to cause
endocrine disruption in some aquatic organisms
(e.g. Matthiessen et al., 2006; Orlando et al., 2004).
In Denmark, steroid hormones from pig manure
have been observed to leach through soil, rapidly
reaching subsurface tile drains at significantly
high concentrations, a process exacerbated by
macropore flow (Kjær et al., 2007). The typically
high connectivity of such agricultural tile drains
to surface waters raises the risk of contamination
of rural streams by EDCs. Endocrine-disrupting
activity has also been documented for certain
pesticides in current use.
Rural housing is often unconnected to municipal
sewage treatment plants and simple wastewater
processing measures such as septic tanks may be
employed. Septic tanks are relatively ineffective
at removing oestrogens from wastewater, and
oestrogenic activities 20 times higher than levels
needed to feminise brown trout have been detected
in discharges from such systems (Stuer-Lauridsen
et al., 2005). Leguminous plants — such as clover,
peas, lupins and alfalfa used as nitrogen-binding
crops for example in organic farming — produce
phyto-oestrogens which may leach to and are
detected in the freshwater environment (Bjerregaard
et al., 2011; Ribeiro et al., 2009).
21
Hazardous substances in water, aquatic biota and sediment
3 Hazardous substances in water,
aquatic biota and sediment — current
concentrations and recent trends
conventions (HELCOM and OSPAR) and European
research studies. However, despite the improved
knowledge base arising from this body of information,
very often uncertainty remains as to whether the
observed concentrations of a particular substance pose
a risk to aquatic environments and human health.
3.1Introduction
This chapter summarises information from a variety
of sources that document the presence of a range of
hazardous substances in Europe's fresh and marine
waters as well as associated biota and sediment.
It describes current concentrations and, where
possible, compares these against existing legislative
criteria. Some recent trends are also identified. The
information is based on data drawn from a variety
of sources, including chemical status as reported
under the RBMPs of the WFD; the EEA's Eionet‑Water
database, which holds freshwater and marine data
reported by EEA member countries; monitoring
programmes conducted by the JRC; regional sea
Map 3.1
-30°
3.2 Chemical status of Europe's water
bodies as reported under the WFD
3.2.1 Surface waters
Under the WFD, Member States were required to
report chemical status for fresh and coastal water
WFD chemical status of surface water as of December 2010
-20°
-10°
0°
10°
20°
30°
40°
50°
60°
60°
Chemical status of
surface water — by
River Basin District —
under WFD reporting
Good
Risk of failure to
achieve good
chemical status
60°
Unknown
Chemical status not
yet reported for RBD
50°
50°
40°
40°
0
500
0°
1000
1500 km10°
20°
30°
Source: EEA based on information reported by Member States in the RBMPs.
22
bodies in 2010 (as part of the RBMPs). Map 3.1
summarises this information for surface waters
at river basin district (RBD) scale and describes
the relative proportion of water bodies of good
status, those at risk of failing to achieve good
status and those of unknown status. The map
reflects information as reported by December
2010. It should be noted that assessment of
these plans is ongoing, and that the conclusions
advanced below remain tentative. Additionally, it
is beyond the scope of this report to present all the
background information supplied in each of the
plans. Consequently, only certain issues have been
highlighted.
Excessive levels of metals including cadmium and
mercury challenge good chemical status in a number
of RBDs to have reported by December 2010,
including those in the Czech Republic, Germany
and the United Kingdom. In Sweden, widespread
excessive levels of mercury in aquatic biota mean
that all RBDs currently fail to achieve good chemical
status. Very few other priority substances in Sweden
are of concern, however, other than locally. In
Sweden, biota has been chosen as the matrix for
monitoring, making detection more likely than in
the water column, given the propensity of mercury
to bioaccumulate. In at least one other Member
Figure 3.1
State, however, a water column (i.e. less stringent)
EQS is known to have been used with respect to
mercury. Such inconsistency in reporting between
Member States is of concern.
PAHs are identified as being problematic, including
in the Elbe and Rhine international river basins,
raising the challenge of how to meet the EQS
given that these substances are primarily released
to and deposited from the atmosphere and can
be transported over long distances. TBT levels in
some UK coastal and estuarine waters threaten
good status whilst a proportion of UK freshwater
bodies are at risk from diffuse pollution by
agricultural pesticides. The Joint Danube Survey 2
was undertaken in 2007 to provide an overview of
status throughout the Danube river system. Whilst
the results do not replace national assessments, they
do provide an indication of chemical status and
have identified DEHP, PAHs, nonylphenol, TBT and
trichlorobenzene as being of concern; 44 % of water
samples exceeded the EQS for DEHP.
3.2.2Groundwater
Good groundwater chemical status is based upon
compliance with EU-wide standards for pesticides
and nitrates and threshold values established by
Number of GWBs at poor chemical status due to cadmium, lead and mercury
Number of groundwater bodies at poor status
40
35
30
25
20
15
10
5
0
Czech
Republic
(161)
Cadmium
Note:
Finland
(3 608)
Lead
France
(560)
Germany
(1 036)
Ireland
(757)
Slovakia
(101)
United
Kingdom
(716)
Mercury
The figures in parentheses indicate the total number of GWBs in each country. The established thresholds vary between
Member States. No groundwater bodies (GWBs) at poor status due to any of these three heavy metals exist in Belgium,
Bulgaria, Estonia, Latvia, Lithuania, Hungary, Malta, Netherlands, Austria, Poland, Romania, Slovenia and Sweden. No
information was reported for any of these three heavy metals in Denmark, Greece, Spain, Cyprus, Italy and Luxembourg.
Source: EC, 2010a.
23
Figure 3.2
Number of GWBs at poor chemical status due to arsenic and tri- and/or
tetrachloroethylene
Number of GWBs at poor chemical status
45
40
35
30
25
20
15
10
5
0
Belgium
(80)
Czech
Republic
(161)
Arsenic
Note: Finland
(3 608)
France
(560)
Germany
(1 036)
3 or 4-chloroethylene (sum)
Hungary
(185)
Ireland
(757)
3-chloroethylene
Netherlands
(23)
Poland
(160)
Slovakia
(101)
United
Kingdom
(716)
4-chloroethylene
The figures in parentheses indicate the total number of GWBs in each country. The established thresholds vary between
Member States.
For arsenic: no GWBs at poor status exist in Bulgaria, Estonia, Latvia, Lithuania, Hungary, Malta, Austria, Portugal, Romania
and Slovenia. No information was reported for Denmark, Greece, Spain, Cyprus, Luxemburg and Sweden. Italy has reported
GWBs at poor status but has not specified a number.
For tri- and tetrachloroethylene: no GWBs at poor status exist in Belgium, Bulgaria, Estonia, Latvia, Lithuania, Malta,
Netherlands, Austria, Portugal, Romania and Slovenia. No information was reported for Denmark, Greece, Spain, Cyprus,
Luxemburg, Poland and Sweden. Italy has reported GWBs at poor status but has not specified a number.
Source: EC, 2010a.
the Member States for other pollutants, as defined
under the Groundwater Directive. Recent reporting
by Member States of those substances that give rise
to poor chemical groundwater status illustrates
that contamination by heavy metals occurs in
some Member States (Figure 3.1) whilst levels of
arsenic (Figure 3.2) and tri- and tetra-chloroethylene
(Figure 3.2) are also observed to sometimes exceed
the established thresholds. However, these thresholds
often vary considerably between Member States. Full
details of this reported information are provided in
EC, 2010a. Pesticides too are observed to exceed the
thresholds, although declining trends are evident, for
example, in German groundwater (UBA, 2010).
3.3 Pan-European monitoring of
organic substances
The JRC has recently organised a large-scale
sampling and monitoring programme at 122 river
stations and 164 groundwater sites in 27 European
countries in order to obtain a pan-European
24
perspective on the occurrence and levels of a range
of organic substances, including many of those
considered to be emerging pollutants (Loos et al.,
2009 and 2010). Emerging pollutants are those for
whom the potential for adverse effects has only
recently become apparent (in contrast, for example,
to metals and organochlorines) and for which the
understanding of sources, emissions, levels and
effects in the aquatic environment remains limited.
Across the JRC study, nearly 60 organic substances
were investigated. These include pesticides,
pharmaceuticals, hormones, antibiotics,
perfluorinated surfactants and other industrial
chemicals. In total, more than 100 collaborators
joined the monitoring campaigns and samples were
analysed in 5 expert laboratories. The information
gathered is of value in determining whether a
particular substance is of pan-European relevance or
if it is a local issue. In addition, technical guidance
and best practice for analysing priority substances
has arisen from the work to support implementation
of the WFD (Lepom et al., 2009; Loos et al., 2009).
However, for several of the monitored substances,
threshold concentrations or environmental quality
standards for freshwater have yet to be set.
3.3.1Rivers
The average frequency of detection for all
compounds in rivers was 61 %, with the
highest median concentrations being found
for nonylphenoxyacetic acid (a degradation
product of surfactants, 233 ng/l), benzotriazole
(an aromatic compound commonly used as a
corrosion inhibitor, 226 ng/l), and carbamazepine
(a pharmaceutical, 75 ng/l). In addition, relatively
high average concentrations (> 50 ng/l) were found
for ibuprofen (a pharmaceutical), nonylphenol (an
alkylphenol used as a surfactant), sulfamethoxazole
(an antibiotic) and isoproturon (a herbicide), whilst
Figure 3.3
the highest maximum concentrations (> 500 ng/l)
were measured for isoproturon, diuron (a herbicide),
nonylphenol and tert-octylphenol (a surfactant) —
all of which are classified as PSs under the EQSD.
Pesticides were generally found at relatively low
concentrations, potentially because the survey
was conducted in autumn. The results for atrazine
broadly support those reported to the EEA.
3.3.2Groundwater
For the groundwater monitoring exercise (Loos
et al., 2010), the list of substances selected for
monitoring in rivers was supplemented by
additional compounds, primarily pesticides. The
average frequency of detection for all compounds
in groundwater was 25 %, with the most frequently
detected including caffeine, perfluorooctanoic
Frequency of detection for selected substances (% of samples) in rivers and
groundwater
Octylphenol
Estrone
Bisphenol A
Nonylphenol
NPE1C
Terbutylazine
Diuron
Isoproturon
Atrazin
Methylbenzotriazole
Desethylterbutylazine
Simazine
Sulfamethoxazole
Carbamazepine
Desethyl-Atrazine
Caffeine
Benzotriazole
PFDA
PFOS
PFNA
PFOA
PFHpA
Diclofenac
Ibuprofen
Mecoprop
Ketoprofen
Bentazone
2,4-Dinitrophenol
Nitrophenol
%
0
20
Groundwater
40
60
80
100
Rivers
Source: Loos et al., 2009; Loos et al., 2010.
25
Box 3.1 The triazine pesticide group
Triazine pesticides are of particular concern with regard to freshwater contamination due to a number
of their properties, including a relatively high water solubility, persistence (long half-life) and low soil
adsorption. Of the triazine pesticides, both atrazine and simazine have been used as herbicides (by
inhibition of photosynthesis) on cropland, on transport highways and domestically. Both, however, have
now been banned and are classified as PSs under the EQSD.
Despite the ban, data reported under Eionet indicate that both pesticides remain evident in
groundwaters across Europe. Map 3.2, for example, illustrates which substances in the triazine group of
pesticides have been found in groundwater in recent years, on at least one occasion, at concentrations
greater than 0.1 µg/l. This is the standard established under both the Groundwater Directive and
the Drinking Water Directive. In addition to atrazine and simazine, both the transformation products
of atrazine — desethylatrazine and desisopropylatrazine — and terbuthylazine, an active substance
replacing atrazine, have also been found at concentrations exceeding the standard (Map 3.2). It should
be noted, however, that the frequency of exceedance for the triazine pesticides is relatively low for all
countries reporting to the EEA. In addition, gradual declines in the frequency of detection of triazine
pesticides have been reported over recent years.
Data reported to Eionet describing concentrations of atrazine and simazine in European rivers indicates
that, for all 16 countries providing data, no exceedance of the EQS is observed. This is likely to reflect
the ban and its relatively quick impact upon river concentrations relative to those in groundwater. In
French rivers, for example, detection of atrazine has fallen from more than 60 % of analyses in 2002 to
about 15 % in 2007.
Map 3.2
-30°
Triazine pesticides in groundwater between 2003 and 2008
-20°
-10°
0°
10°
20°
30°
40°
50°
60°
70°
Triazine pesticides found
in groundwater between
2003 and 2008 at
concentrations above
0.1 µg/l
Substance
60°
Atrazine
Desethylatrazine
50°
Desisopropylatrazine
Simazine
Terbuthylazine
Threshold
concentration
not exceeded
50°
Country
Reported
40°
No data
Outside coverage
40°
0
Note:
500
0°
1000
1500 km
10°
20°
30°
40°
The pie charts indicate the occurrence, on at least one occasion, of concentrations above the limit of 0.1 µg/l. The data
shown do not reflect the frequency with which the threshold has been exceeded.
Source: Data were sourced from Eionet and, in the case of Denmark, supplemented by information from the Danish national
groundwater monitoring programme (1989–2007) and the Geological Survey of Denmark and Greenland.
26
acid (PFOA, a fluorosurfactant), atrazine and
desethylatrazine (DEA, a metabolite of atrazine).
Overall, substances were detected less frequently in
groundwater than in rivers (Figure 3.3), although
some exceptions to this observation were apparent,
notably for simazine (a herbicide), bisphenol A
(an organic compound used to make plastics) and
octylphenol. However, those substances found
with high frequency did not necessarily have the
highest concentrations. Across the survey, 29 %
of all groundwater samples contained at least
one pesticide exceeding the EU limit of 0.1 µg/l
for groundwater and drinking water, for a single
pesticide. In 10 % of samples, the EU limit of 0.5 μg/l
for total pesticides was exceeded.
In addition to the JRC monitoring programme, a
number of recent European research studies have
contributed to a growing, although still incomplete,
understanding of the levels of various hazardous
substances in water, including some of those viewed
as emerging pollutants. These studies include surveys
of pharmaceuticals in freshwater in Spain (Ginebreda
et al., 2010) and the United Kingdom (Ashton et al.,
2004) and heavy metals in the Seine (Meybeck et al.,
2007). A recent survey of PAH levels in the sediment
of high mountain lakes in Europe showed total
concentrations in all lakes to be above the no-effects
threshold (Quiroz et al., 2010). This finding highlights
the challenge of addressing substances that are
largely ubiquitous, subject to transport over large
distances in the atmosphere and detectable in remote
regions away from human activity.
Veterinary medicines have received little attention
with respect to their monitoring within aquatic
environments. One exception is a UK study (Boxall
et al., 2006) involving the continuous monitoring
of water and sediment at farms where veterinary
medicines were known to be in use, in order
to determine typical exposure profiles in rural
streams. Maximum concentrations of antibacterials
in stream water ranged from 0.02 (trimethoprim)
to 21.1 (lincomycin) µg/l, whilst the parasiticides
(doramectin and ivermectin) were not detected.
Concentrations of antibacterials in sediment
were 0.5–813 µg/kg and those of doramectin and
ivermectin were 2.7 and 4.9 µg/kg respectively.
3.4 Transitional, coastal and marine
waters
Riverine loads and direct discharges of hazardous
substances to coastal waters are not, as a rule,
widely reported across Europe, although the
OSPAR regions of the North Atlantic form an
exception. Here data are available for five hazardous
substances, which include three metals (cadmium,
mercury and lead), the insecticide lindane and PCBs,
a group of chemicals previously widely used in
electrical equipment.
Despite some uncertainties in the data and the need
for caution in interpretation, downward trends are
detected for all five substances as regards their total
inputs to the OSPAR region (Figure 3.4; OSPAR,
2009e). For example, statistically significant
downward trends in combined riverine inputs and
direct discharges of mercury to the Greater North
Sea and Celtic Sea regions, of about 75 % and 85 %
respectively, are reported for the period 1990–2006.
The decline observed for the Greater North Sea is
supported by data from the Rivers Elbe, Meuse
and Rhine, all of which illustrate decreases of
65–70 % in riverine inputs of mercury over this
period. Significant downward trends for cadmium
are also apparent; these are attributed to declines
in both riverine inputs and direct discharges.
Reductions to the Greater North Sea region reflect,
in part, a 40 % decline in riverine inputs from the
River Elbe (OSPAR, 2009e). Downward trends in
lead are also observed, with substantial decreases
apparent in the Rivers Rhine and Seine. In addition
to the decline in metal emissions to air (see earlier
case studies), these trends observed in the OSPAR
regions are also attributed to a decline in emissions
to water, both through the implementation of
best available abatement techniques at industrial
facilities and improvements in municipal
wastewater treatment (OSPAR, 2009e). Aside from
the metals, marked declines in lindane and PCBs
are clearly apparent (Figure 3.4), reflecting a ban on
the use of both.
Despite the high number of hazardous substances
with the potential to contaminate the marine
environment, information with sufficient
geographical and temporal coverage to enable a
pan-European assessment is limited. A collation of
data from HELCOM, OSPAR and the EEA member
countries has, however, enabled an assessment
of the levels of seven hazardous substances
in marine biota — in the North-East Atlantic,
the Mediterranean Sea and the Baltic Sea. The
substances include the five previously described
with respect to inputs to OSPAR waters, plus a
further insecticide (dichlorodiphenyltrichloroethane
(DDT)) and a fungicide (hexachlorobenzene (HCB)).
This assessment complements the information
provided within the RBMPs of the WFD with
respect to transitional and coastal waters. It does
not, however, reflect official national assessment of
chemical status.
27
Figure 3.4
Input of hazardous substances (via riverine loads and direct discharges) into the
North-East Atlantic during the period 1990 to 2008
%
150
125
100
75
50
25
Cd
Pb
Hg
Lindane
20
08
20
07
20
06
20
05
20
04
20
03
20
02
20
01
20
00
19
99
19
98
19
97
19
96
19
95
19
94
19
93
19
92
19
91
19
90
0
PCB7
Source:OSPAR.
Maximum levels in fish, molluscs and crustaceans
have been set for the three metals in order to protect
public health (Regulation (EC) 1881/2006). These
maximum levels are used in this analysis (Map 3.3)
to establish the threshold boundary between
moderate and high concentration. For the other
contaminants discussed here, alternative approaches
to establishing such thresholds have been used,
including OSPAR's background assessment
concentration (BAC) and ecotoxicological
assessment criteria (EACs). Trend information
encompasses the period 1998 to 2008.
All seven substances can be found at high
concentrations in all three of these European
seas. In the case of DDT, HCB, lindane and PCBs,
this observation reflects their persistence in the
aquatic environment, given that all four are now
banned within Europe. In certain locations, metal
concentrations exceed the maximum levels set
by legislation. In the Mediterranean Sea, lindane
concentrations exhibit a declining trend, although
some sites show an upward trend in mercury and
lead. In the North-East Atlantic, concentrations
of cadmium, DDT, lead, lindane and PCBs are all
28
declining, reflecting the decrease in riverine loads.
Declining trends are also evident for lindane in the
Baltic Sea, although data from other sources (not
shown) indicate declining trends in PCBs in herring,
perch and mussels in several locations in the Baltic
Sea (HELCOM, 2010).
In the Black Sea (data not featured in Map 3.3),
concentrations of lindane and DDT in sediment
have been found to be five times higher than the
Russian standards for extremely high pollution
(EEA, 2010a). Metal pollution represents a particular
problem in the Danube estuarine region and large
ports, although in some areas concentrations appear
to be decreasing (Korshenko et al., 2008). Petroleum
hydrocarbon pollution in Romanian and Turkish
waters exceeds threshold values by a factor of 16
(EEA, 2010a).
3.4.1 Other hazardous substances in the marine
environment
Whilst Europe-wide data are not available, the
banning of TBT has led to clear downward trends
of concentrations in marine snails in the OSPAR
Map 3.3
Assessment of hazardous substances in biota in the North-East Atlantic Sea,
Baltic Sea and Mediterranean Sea
Cd
0
Hg
1000 km
0
0
1000 km
0
1000 km
PCB
DDT
1000 km
0
1000 km
Aggregated assessment of hazardous substances measured in the North East
Atlantic Sea including the North Sea, Baltic Sea and Mediterranean Sea
Low concentrations
Cd:
Cadmium
Medium concentrations
Hg:
Mercury
High concentrations
Pb:
Lead
HCB:
Hexachlorobenzene
Lindane:
Gamma hexachlorocyclohexane
(Y - HCH)
Mediterranean Sea
DDT:
Dichlorodiphenyltrichloroethane
Black Sea
PCB:
North East Atlantic Sea
Baltic Sea
0
1000 km
Lindane
HCB
0
Pb
Polychlorinated biphenyls
Trend up
1000 km
Trend down
Source: EEA, 2011.
region (OSPAR, 2009a). A similar outcome is evident
in the HELCOM region, with clear declines in TBT
levels in mussels, eelpout and whelks (HELCOM,
2010). In both sea regions, however, high levels of
TBT in sediment are still found locally, reflecting
the historical use and persistence of this substance.
Although European legislation restricts the use of
perfluoroalkyl substances (used as surfactants), they
are widely found in marine birds and mammals in
the Baltic (HELCOM, 2010). Limited information
is available with respect to emerging pollutants in
the European marine environment and, to date, no
Europe-wide monitoring programme — equivalent
to the one undertaken by the JRC for freshwater —
has been launched. However, a growing number
of research studies indicate a potential cause for
concern notably for pharmaceuticals and personal
care products (Näslund et al., 2008; Roberts and
Thomas, 2006; Xie et al., 2008).
3.4.2 The Arctic
Hazardous substances, including persistent organic
pollutants (POPs) and mercury, are present in parts
of the Arctic where there are no human activities to
explain the contamination. This observation shows
that the region acts as a sink for pollutants that have
been transported over long distances, by rivers,
air and ocean currents. Some of these substances
accumulate in marine foodwebs and therefore in
29
30
humans, and their concentrations in both can reach
much higher levels than in water and air.
noted in sea otters from Alaska and ringed seals
and beluga whales from the Canadian Arctic.
International policy efforts have, however,
produced positive effects on the levels of some
substances. The Stockholm Convention on POPs
and the Aarhus Protocol on POPs, for example,
have led to a decline in POPs in Arctic air and
wildlife, although concentrations are still high
enough to affect the health of top predators, such
as polar bears, in the marine food web (AMAP,
2009). Perfluorinated compounds are detected in
Arctic marine life, with an initial increased trend
occurring from the initiation of data collection in
the mid-1980s. A less consistent picture has been
apparent in recent years. Some declining levels of
perfluorooctanesulfonic acid (PFOS) have been
These trends are consistent with the decline in the
production of PFOS; however, there are current
sources that may continue to contribute inputs to
the environment (AMAP, 2009). Brominated flame
retardants are also detected in Arctic marine life, with
increasing trends broadly following the production
and use up to the early 2000s. There is some evidence,
however, that concentrations are starting to level off
or decline, at least in some areas (AMAP, 2009), in line
with restrictions upon the use of these substances in
recent years. Clear declines in riverine load and direct
discharges of lead and cadmium to Arctic waters are
reported, although insufficient data are available with
respect to mercury (OSPAR, 2009e).
Impacts of hazardous substances in water
4 Impacts of hazardous substances in
water
4.1Introduction
This chapter addresses the impacts of hazardous
substances on the health of aquatic ecosystems and
the potential for risks to human health. It reviews
documented detrimental impacts on both freshwater
and marine life and highlights a few substances of
concern. The risks to human health from hazardous
substances in the wider environment are briefly
addressed. However, in line with the central themes
of this report, more detailed analysis is restricted to
the potential for human exposure via water, namely
the chemical contamination of food from aquatic
sources and the contamination of drinking water.
Excessive levels of chemicals in water also give rise
to economic impacts, such as the significant capital
and operating costs associated with water and
wastewater treatment.
at very low concentrations, such levels can still be
sufficient to cause detrimental impacts.
Here, the overview of impacts upon aquatic
ecosystems focuses on documented effects linked to
four groups of substances: pesticides, human and
veterinary medicines, personal care products and
nanomaterials, with the latter three groups falling
into the category of emerging pollutants. In addition
to these aspects, the overview includes an initial
focus upon a particular category of effect in aquatic
biota — the phenomenon of endocrine disruption.
It should be noted that oestrogenic effects can be
caused by a range of chemicals including pesticides
and pharmaceutical products. Combination effects
arising from the presence of several chemicals are
also significant.
4.2.1 Endocrine disruption
4.2 Impacts on aquatic ecosystems
Numerous studies have documented a range of
detrimental impacts of hazardous substances upon
aquatic ecosystems, particularly in freshwater,
estuarine and coastal environments, but also in the
open sea. Observations from aquatic ecosystems in
the 1950s and 1960s were the first 'early warnings'
of the environmental dangers of the widespread
production and use of industrial and man-made
chemicals. The effects, for example, of methyl
mercury, organochlorines and pesticides such as
DDT on seabirds and marine mammals are well
documented (Hario et al., 2004; Helander et al., 2009;
Sørmo et al., 2005).
The early studies identified chemical properties
which were particularly important with respect
to environmental effects and which later became
important criteria for classification and labelling
in chemical legislation. Examples of these are
lipid solubility (lipophilicity, hydrophobicity),
persistence, and bioaccumulation potential. The
mechanism of biomagnification became apparent:
chemicals are enriched higher up in the food chain,
resulting in the highest levels in top predators like
tuna or salmon, fish-eating birds, marine mammals
(seals, dolphins) and eventually humans. With
increased knowledge, concern with respect to new
groups of substances has grown, and whilst these
are often only present in the aquatic environment
The egg yolk protein vitellogenin is used as a
biomarker (i.e. a change in a biological response
at molecular, cellular or physiological level that
can be related to exposure to or toxic effects of
environmental chemicals) for oestrogenic effects.
Increased levels of vitellogenin in the blood of
female or male juvenile fish that are not sexually
mature mean that they have been exposed to
substances with oestrogenic activity. Another sign
of endocrine disruption, also related to oestrogen
exposure, is intersex characterised by the presence
of eggs in the testes of male fish (Jobling et al., 2006;
Nolan et al., 2001).
Numerous studies across Europe document the
occurrence of sexual disruption of freshwater
fish found in the proximity of effluent discharges
from wastewater treatment plants. Jobling et al.
(2006), for example, report that intersex in roach
in the UK was significantly correlated with
predicted concentrations of oestrogens in river
reaches receiving treated sewage effluents. In the
Netherlands, elevated concentrations of vitellogenin
were observed together with an increased
prevalence of intersex in wild male bream in a
small river receiving treated sewage (Vethaak et al.,
2005). Both in situ and laboratory bioassays showed
oestrogenic hormones to be primarily responsible
for these effects. In Spain, vitellogenin was found to
be increased in male carp downstream of a sewage
treatment plant (Petrovic et al., 2002) whilst in Italy,
31
50 % of barbel sampled below a polluted tributary
of the River Po showed intersex gonads (Viganò
et al., 2001). Endocrine disruption of male fish has
also been recorded in the Czech Republic, both in
a polluted stretch of the River Elbe downstream of
three major chemical plants (Randak et al., 2009) and
downstream of the city of Brno (Blahová et al., 2010).
Additionally, laboratory studies have shown that the
combined effects of EDCs can be additive, whereby
such chemicals at levels, individually, below which
any effects can be detected, result in observable
detrimental effects when combined (Brian et al.,
2005). EDCs have been observed to cause effects in
other freshwater biota, including mudsnails exposed
via sediments (Duft et al., 2003), and identified as a
potential factor in the global decline in amphibians
(Hayes et al., 2002).
Endocrine disruption in estuarine and marine
environments has also been documented. Elevated
blood vitellogenin concentrations were observed
in male dab (Scott et al., 2007) and cod (Scott et al.,
2006) caught in open waters of the North Sea. In
both studies, the fish were far out to sea away from
any direct sources of pollution. Larger fish were
found more likely to have elevated vitellogenin
levels, suggesting a gradual accumulation, via
feeding, of oestrogenic compounds in the marine
food chain. Endocrine disruption has also been
detected in tuna and swordfish in the Mediterranean
(Fossi et al., 2002), with the latter being linked to
PCB concentrations in the fish (Fossi et al., 2004). In
the United Kingdom, investigative programmes in
several estuaries have found endocrine disruption
in flounder, a bottom-dwelling flatfish particularly
exposed to any contamination of sediment (Thomas
et al., 2004). The UK research showed that male
flounder caught in industrialised estuaries, receiving
effluent from sewage treatment works and industry,
had elevated concentrations of vitellogenin, with
cases of intersex and testicular abnormalities also
recorded (Allen et al., 1999). Also of note, however,
is evidence of a lessening in the degree of endocrine
disruption over time in some UK estuaries, a finding
in line with improvements to the treatment of
wastewater (Kirby et al., 2004; Kleinkauf et al., 2004).
Improvements have also been noted elsewhere, with
a declining trend in imposex being observed, for
example, in whelks netted in Danish coastal waters
of the Belt Sea (Strand, 2007).
In some cases oestrogenic effects are known to
be irreversible (Rodgers-Gray et al., 2001), and in
severely feminised fish, fertility is reduced, raising
implications for population survival (Jobling et al.,
2002). An illuminating example is the experiment
by Kidd et al. (2007), where a synthetic oestrogen
32
was introduced to a whole lake in the Canadian
Experimental Lake Area for seven years, at
concentrations found in polluted environments
(5–6 ng/l). Male fathead minnows showed clear
signs of feminisation (vitellogenin and intersex),
while altered egg development was observed in
females. Strikingly, within seven years, fathead
minnows were almost extinct from the lake, clearly
illustrating that endocrine disrupters can threaten
the sustainability of wild fish populations.
4.2.2Pesticides
Pesticides are rigorously risk assessed before
being approved for marketing. However, their use,
particularly if it does not follow relevant guidance,
can lead to harmful effects upon non-target
organisms in the wider environment, including
freshwater biota. Aside from the potential for
oestrogenic effects (Tyler et al., 2000), severe
impairment of the nervous system of several
fish species has been observed in Lake Balaton,
Hungary, following the use of deltamethrin, a
synthetic pesticide used for the extermination of
mosquitoes on the shores of the lake (Csillik et al.,
2000).
Insecticide run-off has also been shown to adversely
affect freshwater macroinvertebrates in agricultural
streams. Schulz and Liess (1999), for example, found
that short-term contamination during rainfall events
led to acute effects including the loss of 8 of the
11 common macroinvertebrate species normally
present in a stream, with a significant reduction
in population density of the remaining 3 species.
Beketov et al. (2008) also found that short-term
exposure to pesticides causes long-term changes to
invertebrate communities, whilst a toxicity-related
shift from sensitive to more tolerant or opportunistic
species was observed for aquatic biota exposed to
pesticides in agricultural field drains (De Zwart,
2005).
Despite these and other studies, knowledge of the
ecotoxicological effects of pesticides upon aquatic
biota remains limited. In particular, very little is
known about the impact of products formed by
transformation of the parent pesticide compound or
about the risk of additive or synergistic effects that
may arise from the use of agricultural pesticides in
combination with one another.
4.2.3 Human and veterinary medicines
Human medicines
Whilst concentrations of human medicines in
Europe's water bodies are not likely to be high
enough to cause acute toxicity to freshwater biota,
chronic exposure to low concentrations may
potentially give rise to sublethal effects (De Lange
et al., 2006). Hoeger et al. (2005), for example,
showed that the presence of the anti‑inflammatory
drug diclofenac, at concentrations comparable to
those found in freshwater, caused adverse effects in
the kidneys and gills of trout. Similarly, Triebskorn
et al. (2007) observed effects in the gills, liver and
kidneys of trout and carp exposed to four different
pharmaceuticals, again at environmentally relevant
concentrations.
Documented adverse effects are not limited to
freshwater fish. De Lange et al. (2006), for example,
found a significant decrease in the activity of
G. pulex, a freshwater benthic invertebrate, when
exposed to the antidepressant fluoxetine and the
analgesic ibuprofen. Concern also exists with
regard to the potential for antibiotics and steroid
drugs to cause resistance among natural bacterial
populations (Obst et al., 2006).
Impacts of pharmaceuticals upon marine
organisms have also been observed. The
osmoregulatory ability of the green shore crab
Carcinus maenas was impaired when exposed to
diclofenac (Eades and Waring, 2010), whilst the
antiepileptic drug carbamazepine gave rise to
detrimental effects upon Mediterranean mussels
(Mytilus galloprovincialis) (Martin-Diaz et al., 2009).
In addition, clotrimazole, used for the treatment of
fungal infections, has been shown to impact upon
single-celled algae, the basis of the oceanic food
chain (Porsbring et al., 2009).
Veterinary medicines
Information on the effects of veterinary medicines
on aquatic organisms (fish, invertebrates and algae)
needs to be generated as part of the marketing
authorisation process for veterinary medicinal
products in Europe. Comparison of maximum
measured concentrations with predicted noeffect concentrations for a range of veterinary
medicines indicates that, typically, these substances
probably do not pose a great risk to the aquatic
environment. Exceptions, however, are apparent.
These include antibiotics that are particularly toxic
to cyanobacteria (Halling-Sørenson, 1999) and,
similarly, anti‑parasitic compounds with respect to
invertebrate species (Lopes et al., 2009).
The suitability of standard regulatory studies for
assessing the environmental risks of veterinary
medicines has, however, been questioned, with the
use of other, more subtle and chronic endpoints
being advocated. For example, concerns have been
raised over the potential for veterinary antibiotics
in the environment to select for antimicrobial
resistance in bacterial communities (Boxall et al.,
2003).
4.2.4 Personal care products
Personal care products (often grouped with
pharmaceuticals with respect to their environmental
pathways and impact) include cosmetics, fragrances,
lotions, shampoos, soaps, toothpastes and
sunscreens. They are primarily released to water via
wastewater discharges (Muñoz et al., 2008) although
direct release of sunscreens via bathing also occurs.
As in the case of other emerging substances,
understanding of the effects of personal
care products in aquatic ecosystems remains
incomplete, although some toxicological studies
indicate a potential concern. UV filters used in
sunscreens and cosmetics, for example, have been
shown to cause oestrogenic effects in fish, both
individually (Christen et al., 2011) and in mixtures
(Kunz and Fent, 2006). They are also linked to the
bleaching of corals (Danovaro et al., 2008).
4.2.5Nanomaterials
Nanotechnology has great potential for industry
and society, with a wide range of varied
applications that include electronics, optics, textiles,
medical devices, cosmetics, food packaging, fuel
cells, catalysts, biosensors and environmental
remediation including water treatment technology
(Handy et al., 2008). Nanotechnology is expanding
rapidly, and further research is needed to better
understand the associated risks and to ensure the
protection of human health and the environment
(EC, 2009a). Release of nanomaterials to the
environment occurs via production sites, landfills,
waste incineration plants and wastewater treatment
facilities, with the latter including nanoparticles
in both treated effluent and sewage sludge
(Gottschalk et al., 2009; Limbach et al., 2008).
Little information is available on the environmental
toxicity of nanomaterials, although a growing
number of laboratory studies are adding to the
knowledge base. Such research includes the impact
of manufactured nanomaterials upon aquatic biota,
notably for water fleas (Oberdorster et al., 2006),
fish (Smith et al., 2007) and molluscs (Tedesco
et al., 2010). Once released to the environment,
nanoparticles have the potential to interact
with and alter the bioavailability of hazardous
substances. The bioaccumulation of cadmium in
fish, for example, was found to be enhanced in the
33
Box 4.1 Chemical mixtures in the aquatic environment
Monitoring surveys of European freshwaters show that aquatic organisms are often exposed to a
mixture of hazardous substances in their natural environment. Under current chemical legislation,
however, hazardous substances are tested and risk assessed as single entities and not in the mixture in
which they occur in the environment. As a consequence, the actual risks to aquatic environments could
well be underestimated (Kortenkamp et al., 2009).
There are several possible mechanisms by which substances can potentially interact. They can, for
example, add to each other's toxicity or augment each other's toxicity. It is also possible for one
substance to block the toxicity of another. One of the best-established blocking mechanisms is that of
chelating chemicals, like ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid
(DPTA), which reduce the toxicity of metals like copper or zinc by binding them in strong complexes
which are not bioavailable. EDTA, DPTA and similar substances are added to detergents as so-called
'water softeners', since they also bind calcium.
There is currently intense scientific activity to develop and refine models facilitating predictive
assessments of the environmental hazards associated with such mixtures. So-called component-based
approaches (CBAs) are based on the ecotoxicological characterisation of individual mixture components
and a subsequent linking to the toxicity of the resulting mixture. Such studies often aim to develop
a fundamental understanding of how chemical mixtures behave in relation to the toxicity, modes and
mechanisms of action of their components, the exposure conditions as well as the physiology and
ecology of the exposed organisms. One goal is to develop mixture assessment tools that can be used in
predictive risk assessments, in particular for developing EQSs for chemical mixtures. Another important
aim of CBAs is to provide a rationale on how to identify toxicologically important compounds in complex
environmental samples. CBA studies typically use the concept of concentration addition (CA) and (to a
lesser extent) independent action (IA) to predict the expected mixture toxicity implicitly or explicitly.
Compared to the available data for freshwater and terrestrial systems, the empirical evidence with
respect to the joint action of chemicals in the marine environment is limited. Therefore, it is unclear
whether the special chemistry of natural marine waters in combination with the type of pollutants
typically found in the marine environment has an impact on the predictive power of either concept.
One pattern, however, seems to be common amongst the vast majority of ecotoxicological mixture
studies: the joint mixture toxicity is clearly higher than the toxic effect of each individual compound
at the concentration present in the mixture. This has important implications for the definition of EQSs
for aquatic environments, as it clearly indicates that setting an EQS for an individual substance is a
necessary first step, but that compliance with that standard does not a priori safeguard against mixture
effects.
presence of titanium dioxide (TiO2) nanoparticles
(Zhang et al., 2007), whilst the sorption of a PAH
to nano carbon tube aggregates increased toxicity
to algae and daphnids (Baun et al., 2008). Such
interactions must, therefore, be accounted for in
risk assessments and are a parallel to the issue of
chemical mixtures.
4.3 Human health and chemicals in the
environment
Human exposure to certain chemicals in the
environment has been associated with declining
sperm counts, genital malformation, impaired
neural development and sexual function, obesity
and cancer (EEA, 2010b). Of particular concern
34
are persistent and bio-accumulative substances,
endocrine-disrupting chemicals and heavy metals.
Periods of embryonic, foetal and infant development
are known to be particularly sensitive to chemicals,
and toxic exposure at these times can cause disease
and disability across the span of human life (Gee,
2008; Grandjean et al., 2007). Evidence is growing
that early-life or prenatal exposures are linked to
some adult-onset diseases, and some effects may
even be trans-generational (EEA, 2007). However,
assessing the impacts of chemicals on human health
is highly complex and uncertain, due to differences
in individual vulnerability, the time lag between
critical exposure and (mostly non-specific) health
outcomes, the role of other modifying factors (such
as nutrition or social conditions), and exposure
conditions (typically long-term, low-level exposure
to a mixture of chemicals) (EEA, 2007 and 2010b;
Gee, 2008).
Evidence for human exposure to a range of
hazardous substances is strong and derives, in
particular, from studies using biomarkers, i.e.
measures of chemicals or their metabolites within
a biological matrix. For example, samples of blood
(including that from the placenta), urine, breast
milk, and hair show that numerous chemicals are
found in the human body (Calafat et al., 2009; CDC,
2009; Edginton and Ritter, 2008; Vieth et al., 2005).
These studies have contributed to the growing
recognition that risk assessment needs to account
for the potential synergistic effects of human
exposure to a mixture of chemicals. Cumulative
risk assessment is necessary to avoid a likely
underestimation of risks under the current paradigm
of considering substances on a chemical-bychemical basis (EEA, 2010b). Concern with respect
to 'chemical cocktails' is reflected in recent European
Council conclusions (Council of the European
Union, 2009).
Human exposure to toxic chemicals can occur, in
broad terms, via inhalation, ingestion and direct
contact with skin. The latter can arise from the use
of personal care products and household chemicals
but also via inappropriate handling of industrial
chemicals. Exposure via inhalation is dependent
upon ambient air quality, although indoor air
including household dust plays a role. In addition,
exposure to spray drift of chemicals, including
pesticides, can be of importance locally (RCEP, 2005).
Ingestion via terrestrially grown food can pose a risk
where chemicals have been applied to agricultural
land. The European Food Safety Authority (EFSA)
reports on pesticide residues in food commodities
in the EU, Iceland and Norway. In 2008, more than
70 000 samples of nearly 200 different types of food
were analysed for pesticide residues by national
authorities, with 96.5 % of the samples complying
with the legal maximum residue levels (MRLs)
of pesticides (EFSA, 2008). Human exposure to
veterinary drugs can also occur via crops; antibiotics
in pig manure applied to cropland have been found
to be incorporated, via the roots, within winter
wheat (Grote et al., 2007). Hazardous substances
found within treated biosolids arising from
municipal wastewater treatment can also potentially
raise concerns for human health where those
biosolids are subsequently applied to agricultural
land (Clarke and Smith, 2011). However, European
limits have been set for the levels of metals in sludge
intended for agricultural use. Certain chemicals can
also contaminate foodstuffs via their migration from
packaging.
Chemical contamination of food from seafood and
freshwater fish also presents a risk, although this
needs to be balanced against the health benefits of
consumption (Gochfeld and Burger, 2005; Sioen
et al., 2008). Further risk is associated with untreated
or inadequately treated drinking water, and the
potential for exposure via these two water-related
pathways is explored in more detail in the following
section. Despite some research (e.g. Fromme et al.,
2009) understanding of the relative risk posed
by each of the exposure routes outlined above
remains largely incomplete, with a general lack of
quantitative information.
4.4 Human exposure to hazardous
substances via water
4.4.1 Contaminated seafood and freshwater fish
Persistent hazardous substances found in aquatic
environments can bio-accumulate throughout the
food chain, raising implications for human health
with respect to the consumption of seafood (fish,
crustaceans, molluscs and marine mammals)
and freshwater fish. The bio-accumulation of
mercury and various POPs in particular can cause
health concerns for vulnerable population groups
(EC, 2004; EFSA, 2005). Dietary mercury, for
example, is almost completely absorbed into the
blood and distributed to all tissues including the
brain. It also readily passes through the placenta to
the foetus and foetal brain (Sundseth et al., 2010),
with women of childbearing age being regarded as
the population group of greatest concern (Mergler
et al., 2007).
The Arctic provides a prominent example of the
exposure of humans to hazardous substances
through the consumption of food from the marine
environment. Monitoring of contaminant levels
in the Arctic population over the past decade
indicates that human exposure to POPs and metals
is declining, reflecting reduced environmental
contamination, dietary changes (most dietary energy
now comes from store-bought supplies rather than
from traditional food sources in the Arctic (AMAP,
2009)) and health advice to vulnerable population
groups. Human biomonitoring data for PCBs,
mercury and lead indicates that the percentage of
women whose test results exceed health guidelines
is declining over time. However, despite the
declines, more than 75 % of women sampled in
Greenland exceed the US evaluation levels for
mercury of 5.8 mg per litre of blood. In addition,
over a third exceeds the Canadian increased risk
range threshold of 20 mg/l (AMAP, 2009).
35
A number of European studies examining the
potential for exposure to hazardous chemicals via
seafood have been undertaken, with the results
varying with region, population group and the
substance of concern. In the Baltic Sea, for example,
organochlorine levels in salmon and herring were
found to exceed EU maximum permissible levels
(Isosaari et al., 2006), with Finnish consumption levels
of herring likely to exceed recommended intake
limits for these substances (Kiljunen et al., 2007). The
EU limits for mercury are exceeded in blue mussels
of Horsens Fjord, Denmark (HELCOM, 2010). In
Flanders, exposure of recreational fishermen to
PCBs through eel consumption is of concern, with
the Belgian PCB standard for fish being exceeded in
80 % of sampled localities (Bilau et al., 2007). In Italy,
levels of dioxin-like PCBs were found to be twice as
high in farmed sea bass as in those caught wild, a
finding attributable to contaminated feed with respect
to the former (Carubelli et al., 2007). In a Norwegian
study, seafood was found to be a major source of
perfluorinated compounds in humans; however,
tolerable daily intakes were not exceeded (Haug et al.,
2010). In Catalonia, average exposure of children to
a range of contaminants through fish and seafood
consumption was found not to exceed tolerable daily
intake (Martí-Cid et al., 2007), whilst organochlorine
compounds in seafood from the Spanish Atlantic
south-west coast were also below EU regulatory
levels (Bordajandi et al., 2006).
36
cause non-compliance but were often covered by
derogations during this reporting period (EC, 2007).
In recent years, concern has been raised with respect
to the presence of some emerging pollutants within
treated municipal drinking water. In the United
States, for example, pharmaceuticals and endocrine
disrupter compounds have been found in drinking
water distribution systems (Benotti et al., 2009)
whilst the presence of pharmaceuticals in drinking
water in Europe has also been documented (Sadezky
et al., 2008). Pharmaceuticals have also been
detected in bottled mineral water (Perret et al., 2006).
Understanding of the effects of long-term human
exposure to trace amounts of such substances — in
concentrations of parts per billion or trillion —
remains incomplete.
4.4.2 Contaminated drinking water
In some, typically rural, areas of Europe, the
local population relies upon small individual or
community-managed non-piped supplies of water,
usually wells or boreholes. Such small-scale supplies
are not covered by the Drinking Water Directive
and the provision of safe drinking water can present
a challenge: any chemical (or microbiological)
pollution of groundwater in the vicinity of such
wells will pose a threat to public health. The
World Health Organization reports that chemical
contamination of drinking water across the (WHO)
pan-European region, whilst restricted to specific
local areas, can have a significant impact upon
human health (WHO, 2010).
The Drinking Water Directive (and comparable
non-EU legislation) sets quality standards for
water at the tap, based on guidelines issued by the
World Health Organization (WHO), for a range of
microbiological and chemical parameters. Much
of Europe is now connected to municipal systems
supplying treated water under quality-controlled
conditions. However, reporting under the Directive
(for the period 2002–2004) indicates some noncompliance with respect to a range of chemical
parameters including iron, manganese, aluminium,
arsenic, trihalomethanes, lead, nickel, PAHs
and chloride. In addition, individual pesticides
Nitrates in drinking water represent a special
case. Whilst not considered a hazardous substance
according to the meaning of the term in this report,
excessive levels of nitrate in ground and drinking
water raise health concerns, in particular for infants,
young children and pregnant women. Excessive
exposure to nitrates in water in infants and young
children can cause deficiencies of oxygen transport
in blood (methaemoglobinaemia) leading to 'blue
baby' syndrome. Contamination of well water
with nitrate occurs across Europe, and cases of
infant methaemoglobinaemia have been reported
(WHO, 2011).
Protecting Europe's fresh and marine waters from chemical pollution
5 Protecting Europe's fresh and marine
waters from chemical pollution
5.1Introduction
A range of EU, regional and national legislation has
been implemented in Europe to address the use of
chemicals and their emission to the environment,
including fresh and marine waters. Collectively
this legislation aims to reduce risks to human and
ecosystem health through a variety of approaches,
which include bans on production; restrictions
on marketing and use; public participation and
the raising of public awareness; requirements to
demonstrate implementation of clean production
and best available techniques in applications for
industrial permits; requirements with regard to the
disposal of waste; fiscal instruments; the obligation
for producers and importers to prove that their
chemical substances are harmless; emissions
standards including the requirement to reduce
or, in some cases (e.g. PHSs), cease discharges,
emissions and losses of hazardous substances to
water; and the establishment of EQSs for aquatic
ecosystems.
A number of elements in this suite of legislation
require or encourage the control of hazardous
substances at source, an approach generally more
cost-effective than treatment following release. The
possibilities for source control are varied and often
specific to particular pollutants. Examples include
the implementation of legislative limits for the
amount of zinc in tyres and construction materials,
and the use of available alternatives to replace
copper in brake linings, roofs and water pipes
(RIVM, 2008b).
Photo: © Hans‑Christian Holten Lützhøft, (DTU Environment)
37
Box 5.1 Reducing emissions of priority substances in the urban environment
The 'Source control options for reducing the emissions of priority substances' (ScorePP) project has
explored the effectiveness of emission control strategies (ECSs) at reducing emissions of priority
substances within the urban environment. The approach involves the development of semi‑hypothetical
case cities (SHCCs) which draw upon characteristics of actual cities, for example with respect to
wastewater treatment, supplementing them with additional information through expert judgement. In
this way, various ECSs can be explored in a consistent manner across a set of differing city types that
are realistic and representative of the real world. Emissions throughout each city are estimated using
substance flow analysis.
In this example, ECSs are explored within a city (population 0.5 million) broadly typical of northern
Europe. The city is characterised by a consumer‑orientated industry and secondary wastewater
treatment, with 90 % of stormwater being collected in a combined sewer system. Six different ECSs
were applied to the city. The first (ECS1) reflects a business‑as‑usual scenario where no additional
measures (to the current situation) are taken to reduce emissions. ECS2 reflects a strategy where all
relevant EU Directives are fully implemented, including the Sewage Sludge Directive, the Directives
restricting certain hazardous substances in electrical and electronic equipment and the subsequent
disposal and recycling of such equipment, and the Urban Waste Water Treatment Directive (although in
this particular city type, full compliance has almost been achieved already under the business‑as‑usual
scenario). In addition, best available technologies (BATs) are assumed to have been implemented
where required, i.e. in larger industries. ECS3 focuses on voluntary options including educational and
information campaigns, whilst ECS4 extends the BAT requirements to small enterprises. ECS5 focuses
upon stormwater management practices (Scholes et al., 2008) including a reduction in the amount
of impervious urban land to allow for infiltration of water and pollutants as well as enlargement of
stormwater ponds to reduce CSO discharges. Finally, ECS6 addresses advanced wastewater treatment
including oxidation processes and ultra‑filtration.
Figure 5.1
The effects of applying various control options upon emissions of cadmium
and DEHP in the urban environment
Cadmium load, kg
Total load, %
100
250
DEHP load, kg
Total load, %
100
12 000
200
10 000
75
75
8 000
150
50
4 000
25
50
50
6 000
100
25
2 000
Note:
ESC4
l
ta
To
n
at
io
n
tr
at
io
In
ESC5
ESC6
See text for an explanation of each scenario (ESC). 'Surface water' also includes releases to the urban surface. 'Sludge'
includes sludge from both WWTPs and CSOs. 'Infiltration' includes both stormwater sediment and infiltration to the
groundwater. Changes in predicted load (kg) are provided for the various components of the urban environment
(1st Y‑axis), whilst the percentage change in total load is read from the 2nd Y‑axis.
Source:ScorePP.
38
fi l
Sl
e
ac
Su
rf
ESC3
D
eg
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ud
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at
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Ai
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ESC2
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ESC1
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0
0
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Box 5.1 Reducing emissions of priority substances in the urban environment (cont.)
The results of the ECS analysis are illustrated here (Figure 5.1) for two pollutants — cadmium and DEHP
— in terms of their emissions (load) to surface water and air, their infiltration and build‑up in sludge,
and their degradation (which covers wastewater treatment removal processes like biodegradation and
advanced oxidation processes). For both substances, a 15–20 % total reduction in emissions occurs,
relative to business as usual, if EU legislation is fully implemented, whilst a further 15–20 % reduction
occurs under the voluntary option strategy. A substantial decline in DEHP emitted to surface water
and built up in sludge is predicted when BATs are extended to small enterprises. Both stormwater
management practices and advanced wastewater treatment also lead to reduced emissions to surface
water, although the latter results in increased levels of both substances in sludge. The performance of
measures such as stormwater retention ponds and advanced wastewater treatment can vary with the
type of hazardous substance.
Source controls for pharmaceutical products include
the provision of advice on, and mechanisms for,
the appropriate disposal of unused medicines
and containers. Such advice could also include
information on the environmental effects of
inappropriate disposal. Opportunities also exist to
implement green-pharmacy methods, including
a reduction in the environmental impact of
pharmaceutical manufacture and the creation of
active ingredients which decline after use (EEA,
2010c; Kümmerer, 2007). Controls on the use of
pesticides are described in section 5.5. Some source
control measures are more generic and potentially
applicable to a number of groups of substances.
A key measure for reducing the level of purification
required for Europe's drinking water, for example,
is the establishment of safeguard or protection
zones around the source. Such zones, recognised
in the WFD legislation, need to be associated with
regulatory powers to control polluting activities.
Whilst controls at source need to be fully exploited,
full compliance with legislation is likely to also
necessitate the implementation of various other
measures to attenuate the emission of hazardous
substances to water. Such measures include
advanced wastewater treatment, urban stormwater
controls and certain agri-environmental practices.
Advanced treatment of municipal wastewater, for
example, has been shown to significantly reduce
the presence of endocrine-disrupting substances
in treated effluent discharged to receiving waters
(Andersen et al., 2003; Stuer-Lauridsen et al., 2005).
In addition, advanced physical, chemical and
biological methods of wastewater treatment can
remove pharmaceuticals (EEA, 2010c). Revision of
Swiss water protection legislation is currently being
considered to specifically address greater removal
of substances such as personal care products and
pharmaceuticals through upgraded wastewater
treatment (FOPH/FOEN, 2010).
A comprehensive review of all chemicals-related
legislation in Europe is beyond the scope of this
report. Instead this chapter focuses upon the key
Europe-wide legislation that directly or indirectly
addresses the contamination of water by hazardous
substances. Whilst such water-related legislation
is comprehensive, significant challenges remain,
not least because some of the problems currently
observed with respect to chemical contamination
of Europe's aquatic environments relate to two
aspects that are very difficult to address: past uses
of substances that have led to accumulation within
soils and aquatic sediments, and the continuous
release of substances in consumer products.
5.2REACH
EC Regulation 1907/2006 on the Registration,
Evaluation, Authorisation and Restriction of
Chemicals (REACH), managed and coordinated
by the European Chemicals Agency, aims to
improve the protection of human health and the
environment from the risks of chemicals. REACH
gives greater responsibility to industry to manage
the risks from chemicals and to provide safety
information on substances used. Manufacturers
and importers are required to gather information
on the properties of their chemical substances
to allow their safe handling and to register this
information in a central database. The Regulation
also calls for the progressive substitution of the
most dangerous chemicals once suitable alternatives
have been identified. Authorisation is required
for use of chemicals that cause cancer, mutations
or problems with reproduction (CMR), that are
persistent, bioaccumulative and toxic (PBT) or
very persistent and very bioaccumulative (vPvB),
or that are identified from scientific evidence as
causing probably serious effects on humans or the
environment.
39
Box 5.2 Aquatic toxicity testing
Information on aquatic toxicity is mandatory when introducing new chemicals on the market. REACH
requires a 'base‑set' of aquatic toxicity tests for chemicals produced or marketed at more than
10 tonnes per year. Base‑set testing builds on acute toxicity tests with algae, a crustacean (Daphnia
magna) and fish. In an acute toxicity test, organisms are exposed to different concentrations of
the chemical, and the concentration killing or having a defined effect on 50 % of the organisms
is established (LC‑50 or EC‑50). LC‑50 or EC‑50 is a key piece of information when making the
environmental risk assessment. For chemicals below 100 tonnes per year, acute toxicity is enough, but
for chemicals produced or marketed above this rate, additional tests are required to assess endpoints
more subtle than death. Examples of such endpoints are reproduction, multi‑generational survival,
growth of juveniles and vitellogenin induction. In order to standardise the testing, the Organisation for
Economic Co‑operation and Development (OECD) has developed and published a number of testing
guidelines.
5.3 Water Framework Directive
(WFD) and Environmental Quality
Standards Directive (EQSD)
The WFD, which represents the single most
important piece of EU legislation relating to the
quality of fresh and coastal waters, aims to attain
good ecological and chemical status by 2015. The
WFD includes a strong economic component and, in
accordance with the polluter pays principle, requires
that Member States implement cost recovery of the
environmental and resource costs of water services.
The implementation of cost recovery for wastewater
treatment services could help to promote the control
of hazardous substances at source, thereby reducing
their levels in both treated effluent and biosolids at
municipal plants.
The chemical status of Europe's surface waters is
addressed by the EQSD, a 'daughter' directive of
the WFD. The EQSD defines environmental quality
standards (EQSs) in fresh and coastal waters for
pollutants of EU-wide relevance known as priority
substances (PSs). The EQSs associated with the PSs
are defined both in terms of annual average and
maximum allowable concentrations, with the former
protecting against long-term chronic pollution
problems and the latter against short-term acute
pollution. Member States are required to monitor
the PSs in surface water bodies and to report EQS
exceedances. PSs designated thus far include metals,
herbicides, insecticides, fungicides, biocides, volatile
organic compounds, alkylphenols, PAHs and
phthalates. The European Commission is required to
review the list of PSs every four years and identify,
where appropriate, new PSs or PHSs and any need
to revise the EQSs or the status of existing PSs.
The EQSs must not only protect freshwater and
marine ecosystems from possible adverse effects
40
of hazardous substances; they must also safeguard
human health, which potentially can be put at
risk via drinking water or the ingestion of food
originating from aquatic environments. In this way,
all direct and indirect exposure routes in aquatic
systems are to be accounted for when establishing
the EQSs. For example, the setting of an EQS
for the water column alone may be insufficient
with respect to a chemical with a tendency to
bioaccumulate and one which may therefore pose
a risk through secondary poisoning resulting from
food chain transfer. Instead, in this case, a biota
standard may be required alongside the water
column EQS. The technical guidance on deriving
EQSs in the field of water policy has recently been
revised.
In the vicinity of point discharges, concentrations
of pollutants are usually higher than the ambient
concentrations in water. Member States are able
to make use of 'mixing zones' adjacent to the
discharge point where the EQS can be exceeded
so long as the compliance of the rest of the body
of water with the relevant EQS is unaffected. The
extent of mixing zones should be restricted to the
proximity of the point of discharge and should be
proportionate. Technical guidelines with respect
to the identification of mixing zones have been
established (EC, 2010b).
Some pollutants have been designated as
priority hazardous substances (PHSs) due to their
toxicity, their persistence in the environment and
bioaccumulation in plant and animal tissues, or
an equivalent cause for concern. The cessation or
phase‑out of discharges, emissions and losses of
PHSs to the aquatic environment is required within
20 years of the date of the adoption of measures.
Related to this, the Directive also requires each
Member State to establish an inventory of emissions,
discharges and losses for each river basin district
or part of a river basin district in its territory. This
inventory is to address both diffuse and point source
emissions of all PSs. Industrial emissions will be
a fundamental part of the inventory and, as such,
reporting under E-PRTR can provide an important
component. Improved reporting of emissions to
water will, however, be required under E-PRTR for a
number of chemicals.
For substances identified as being of concern
at local, river-basin or national level (known as
river basin specific pollutants) but not as a PS or
PHS at EU level, standards are set by national
governments and the results of monitoring
are considered in the assessment of ecological
status under the WFD. Thus far, relatively little
information has been reported with respect to the
specific pollutants within the RBMPs. In Germany,
however, EQSs have been set for a range of specific
pollutants (UBA, 2010).
The WFD objective of good groundwater chemical
status is directly supported by the Groundwater
Directive (GWD), which has established EU-wide
groundwater quality standards for two groups of
pollutants (nitrates and pesticides). However, for
other pollutants, the establishment of standards
at Community level has not been adopted, due
to the inherent high natural variability caused by
hydrogeological conditions, background levels,
pollutant pathways and interactions with different
environmental compartments. Consequently, for
these other pollutants, the GWD requires Member
States to establish their own groundwater standards,
to be set as threshold values.
These thresholds are primarily based on two
criteria, which respectively address the protection
of associated aquatic ecosystems and groundwaterdependent terrestrial ecosystems, and the protection
of water used for drinking and other purposes. To
date, the thresholds established for some pollutants
(e.g. arsenic, cadmium and mercury) vary markedly
between Member States (EC, 2010a). In 2013, the
European Commission is obliged to undertake a
review of information reported under the GWD and
identify whether additional pollutants should be
regulated at EU level.
5.4 IPPC and E-PRTR
Emissions of hazardous chemicals from industrial
installations and agricultural activities are regulated
in the EU through the Integrated Pollution Prevention
and Control (IPPC) Directive. Abatement strategies
implemented under the IPPC Directive have led to
reductions in metal emissions to both water and air.
The Directive is based on several principles:
1) an integrated approach whereby permits account
for the whole environmental performance of a
plant including emissions to air, water and land,
generation of waste, use of raw materials and
energy efficiency,
2) the dependence of permit conditions upon
implementation of best available technologies
(BATs),
3) flexibility, enabling licensing authorities to
account for the technical characteristics of the
industrial plant, its geographical location and
local environmental conditions,
4) public participation and transparency
including access to permits and results from
the monitoring of releases as reported under
the European Pollutant Release and Transfer
Register (E-PRTR).
The register implements, for the European
Community, the UNECE PRTR Protocol to the
Aarhus Convention on Access to Information,
Public Participation in Decision-making and Access
to Justice in Environmental Matters. Besides the
requirement to report data on industrial emissions
including wastewater treatment plants, E-PRTR is
to now also contain information on diffuse releases
to water. In 2007, the European Commission
proposed a new directive on industrial emissions
integrating seven existing directives, including the
IPPC Directive, into a single legislative instrument,
streamlining permitting, reporting and monitoring
requirements.
5.5
Sustainable use of pesticides
The thematic strategy for the sustainable use of
pesticides provides a framework for minimising the
hazards and risks to health and the environment
stemming from the use of pesticides. Some of the
measures contained in the strategy can be integrated
into existing policy and legislation, but for others, this
is not possible. These measures form the basis of a
new framework directive 'to achieve a sustainable use
of pesticides'.
The Pesticides Framework Directive (2009/128/EC)
contains a number of rules, including the
establishment of national action plans to set objectives
41
in order to reduce hazards, risks and dependence
on chemical control for plant protection. Source
control measures have been identified that will
result in a reduced use of pesticides, including
the encouragement of low-input or pesticide-free
cultivation, prohibition of aerial spraying under
certain circumstances, and the definition of areas of
significantly reduced or zero pesticide use in line with
measures taken under other legislation, for example
the Habitats Directive. In addition, the potential to
reduce the amount of harmful active substances
by substituting them with safer alternatives is also
recognised.
the criteria necessary to achieve good environmental
status for Europe's seas (EC, 2010c). Two of these
relate directly to chemical pollution. Descriptor
8 of the Decision requires that concentrations of
contaminants including the PSs of the EQSD be at
levels not giving rise to pollution effects. Descriptor
9 specifies that contaminants in fish and other
seafood for human consumption may not exceed
levels established by EU legislation or other relevant
standards.
Furthermore, the legislation identifies specific
measures to protect the aquatic environment from
pesticide pollution and thus supports the WFD. These
measures aim to attenuate pesticides along their
transport pathways and include vegetated buffer
strips adjacent to water courses — research studies
indicate that such measures can lead to substantial
reductions in pesticide concentrations in surface
waters (for example as shown in the Footprint study).
In addition, substantial reductions in pesticide use
have been shown to be possible with little or no
impact upon profitability or productivity. This is
achievable, for example, through modification of crop
rotations and sowing dates, and through the selection
of more pest-resistant crop varieties. Implementation
of the Pesticides Framework Directive is required to
support the attainment of good chemical status under
the WFD, although national legislation also has a role
to play in limiting pesticide levels. Denmark's green
growth action plan, for example, has set a limit for
the frequency with which pesticides are applied to
agricultural land.
Both OSPAR and HELCOM have strategic objectives
of preventing pollution of each convention area by
continuously reducing discharges, emissions and
losses of hazardous substances, with the ultimate
aim of achieving concentrations in the marine
environment that approximate background values
for naturally occurring substances and lie close to
zero for man-made synthetic substances.
Complementing the strategy and the Framework
Directive, Regulation (EC) 1107/2009 provides
harmonised, strict rules for the authorisation of plant
protection products, including the requirement for
risk assessments for effects on human health and the
environment to be carried out before a product can be
placed on the market.
5.6 Marine Strategy Framework
Directive
The Marine Strategy Framework Directive (adopted
in June 2008) was introduced to protect Europe's
marine environment more effectively. It aims to
achieve good environmental status of the EU's
marine waters by 2020 and to protect the resource
base upon which marine-related economic and
social activities depend. In September 2010, the
European Commission adopted a decision outlining
42
5.7 Regional Sea Conventions
5.8 Substance-specific legislation
Aside from the Pesticides Framework Directive, a
wide range of legislation — specific to a particular
substance or group of substances — has been
implemented in the European Union to protect
human and environmental health. Examples include
legislation relating to the production, use and
disposal of PCB, which has resulted in declines in
concentrations found in marine biota (HELCOM,
2010). A similar outcome has resulted from the
banning of TBT in anti‑fouling paints, although high
levels in marine sediments can still be observed
in certain locations (HELCOM, 2010). Numerous
other examples exist, such as directives restricting
certain hazardous substances in electrical and
electronic equipment and the subsequent disposal
and recycling of such equipment, controls on the
marketing and use of nonylphenols, regulations on
the use of biocides and, very recently, a ban on the
use of bisphenol A in infant feeding bottles.
Marketing authorisation for human medicinal
products requires that an environmental risk
assessment be undertaken, in accordance with
directives established in 2001 and subsequently
amended in 2004. However, the results of this
assessment are not considered in the risk-benefit
balance that is the basis of the authorisation.
Moreover, products authorised before 2004,
such as ibuprofen, which is widely detected
in surface water, did not have to undergo an
environmental risk assessment. The Directive also
calls for appropriate collection systems to be set
up for medicinal products that are unused or have
expired. Such systems, however, do not appear
to have been implemented in a suitable way in all
Member States. A recent regulation (EC 1235/2010)
on pharmacovigilance with regard to medicinal
products for human use identifies the pollution of
water and soils with pharmaceutical residues as an
emerging problem for which the Member States
should consider measures to monitor and evaluate
the risks of environmental effects, including those
which may have an impact upon human health.
environmental risks of veterinary products should
be assessed have been produced (CVMP, 2007). The
approach used in Europe is a two-phase process.
In phase 1, the potential for the environment to be
exposed to the veterinary product is determined.
For compounds that do not pass the phase 1 check,
information on their effects on terrestrial and aquatic
organisms is required. Recommended aquatic
studies include acute toxicity studies on daphnia
and fish, with mortality as the test endpoint, and
short-term studies of the effects of the compound on
the growth of green or blue-green algae.
An environmental risk assessment has been required
for all new veterinary medicinal products since
the mid-1990s. Recently, manufacturers of generic
medicines have also been required to assess the
environmental risk of their products, and therefore
information on older compounds is increasingly
becoming available. Guidelines describing how the
Aside from specific European legislation,
internationally binding instruments have been
established. They include two instruments that
address the reduction and/or elimination in
production, use and release of persistent organic
pollutants (POPs): the Aarhus Protocol on POPs and
the Stockholm Convention on POPs.
43
Improved assessment and modelling tools
6 Improved assessment and modelling
tools
Assessments of the levels and effects of hazardous
substances in the aquatic environment are
complicated by an underlying dilemma. A focus
upon determining the concentration of a few
pre‑selected PSs bears a strong risk of missing
other important (including emerging) problematic
substances. In addition, such an approach
disregards the effects of chemical mixtures and
interactions with other stressors, thereby further
diminishing the likelihood of reliably linking
cause with biological effect. However, it is neither
practical nor affordable to sample and analyse
at sufficient spatial and temporal resolution for
hundreds of individual substances within fresh
and marine waters, including the water column,
sediment and aquatic biota.
To improve this situation, recent European research
studies (e.g. Modelkey) have led to the development
and testing of new assessment and modelling
tools that help to link chemical contamination
with observed deterioration of ecological quality
in freshwater ecosystems. Such tools include
innovative approaches to the evaluation of existing
chemical and biological monitoring data, together
with site‑specific experimental techniques to
establish cause‑effect relationships.
For example, the 'Species at risk' (SPEAR)
index (Liess and von der Ohe, 2005), a novel,
stressor‑specific indicator for the presence of
invertebrate species sensitive to organic toxicants in
an aquatic ecosystem, helps to diagnose toxic stress
in aquatic communities even in the presence of other
stressors. It has been shown for different river basins
that the reduction of SPEAR, reflecting for example
the disappearance of benthic invertebrates, is
correlated with increasing contamination expressed
as toxic units based on the toxicity to Daphnia magna
as a standard test organism (Figure 6.1; von der Ohe
et al., 2009). The relationships derived also capture
the impact of confounding factors such as the
recovery potential due to non‑impacted upstream
sites that allow for the re‑colonisation of affected
water bodies. The toxic unit approach is based on
concentration addition as a widely accepted model
for mixture toxicity and considers the whole range of
monitored compounds. Both the SPEAR index and
the toxicity units approach are generally applicable to
biological and chemical monitoring data, respectively,
with the latter addressing the reality of exposure to
44
mixtures in the aquatic environment. At present, a
SPEAR index for organic toxicants and pesticides
has been established and validated; however, several
new indices specific to other stressors are under
development.
Where no toxicity data for monitored substances are
available, quantitative structure‑activity relationship
(QSAR) models help to fill the gaps (von der Ohe
et al., 2011), correlating biological activity with
chemical structure. As an alternative approach,
the effect and probable cause (EPC) model may be
applied to estimate deviations of communities from
a reference situation (i.e. where there is an absence
of significant human disturbance or alteration)
and the contribution of different stressors to this
effect (de Zwart et al., 2009; Posthuma and de
Zwart, 2006). Toxic contamination is translated to
multi‑substance 'potentially affect fractions' (msPAF)
based on mixture toxicity and species sensitivity
distributions. Thus msPAF reflects an estimate of
Figure 6.1
Relationship between the
presence of sensitive species
expressed as SPEAR and the
contamination expressed as
the sum of toxic units (TUs)
towards Daphnia magna as the
reference organism
SPEAR (%)
80
60
40
20
b
0
–4
–3
–2
Log TUSum Daphnia magna
Sites with recovery potential
Sites without recovery potential
Source: Liess and von der Ohe, 2005.
–1
0
the number of species that will be lost due to the
measured contamination. The EPC model enables
the relative contribution of different causes (multiple
stressors) of the loss of species to be quantified in a
river basin.
For the estimation of downstream risks of pollution
from point discharges, a generic exposure model
widely applicable to river basins has been developed
(van Gils et al., 2009). It establishes spatial relations
between pollution sources and ecological risks
taking into account the geometry, hydrology, and
fine sediment dynamics of European river basins. In
addition, the model accounts for bio‑accumulation
and biomagnification, so that impacts up to the
level of top predators (secondary poisoning) can be
assessed.
For the identification and confirmation of toxic
effects and individual toxicants as the cause of these
effects, a number of experimental tools are available.
These are valuable, for example, where the chemical
status of a water body is apparently classified as
'good' in terms of PSs and EQS, but where biological
quality is known to be poor. In other words, in
locations where it remains unclear as to whether one
or more non‑PS (of which there may be hundreds in
an individual sample) are a causal factor.
Numerous in vitro and in vivo assays together with
a set of biomarkers are available for trophic level or
mode‑of‑action related identification and assessment
of effects. These tools can be used, therefore, to
verify that chemicals are a causative factor in the
Figure 6.2
observed biological deterioration. If the assays do
not verify chemicals as a causal factor, non‑chemical
stressors are likely to be primarily responsible for
the biological deterioration and further assessment
can be focused in this direction. If, however, a
chemical cause is established, effect‑directed
analysis (EDA) of relevant toxicants combines the
bioassays with fractionation and chemical analysis
as well as structure elucidation to determine
the underlying causes, including previously
unsuspected chemicals contributing to the effects
of the complex mixture (Figure 6.2; Brack, 2003).
Selection of sites representative of a river basin
is important with respect to the EDA approach;
ideally, sampling should occur downstream of major
sources of pollution but also in integrative sinks
such as reservoirs, harbours or estuaries, particularly
for sediment‑associated substances.
Application of EDA to sediment extracts from
major European rivers suggests that the role of
semi‑polar and polar compounds has, to date,
been significantly underestimated in sediment
risk assessments focused on metals and non‑polar
compounds such as PAHs, PCBs and chlorinated
pesticides (Lübcke‑von Varel et al., 2011). EDA
focusing on algal growth inhibition, mutagenicity,
tumour promotion and endocrine disruption as
endpoints has suggested a clear dominance of polar
fractions causing these effects. The attribution of
impacts to more polar compounds was strengthened
when bioavailability was considered in the analysis.
This has been shown, for example, for the biocide
triclosan, which is used in many personal care
Scheme of effect‑directed analysis
Environmental
contamination
Biological
Chemical
analysis
analysis
Confirmation
Fractionation
Biological
analysis
Toxicant
Source: Brack, 2003.
45
products and released via wastewater treatment
plants. Triclosan has been identified as a major
toxicant to green algae in contaminated sediment
despite the co‑occurrence of great concentrations
of PAHs and other classical sediment contaminants
(Bandow et al., 2009).
EDA has been particularly successful in identifying
endocrine disrupters such as oestrogenic (Thomas
et al., 2001) and androgenic compounds (Thomas
et al., 2002; Weiss et al., 2009a). Natural oestrogenic
steroids together with the synthetic contraceptive
pill component 17α‑ethinylestradiol discharged
primarily from wastewater treatment plants
have been identified by EDA as major oestrogens
in water samples and fish bile (Houtman et al.,
2004; Thomas et al., 2001). Based on these
findings, these compounds were taken into
consideration in monitoring, risk assessment
and technological improvements for wastewater
treatment plants. Other examples include the
identification of naphthenic acids as important
in vitro xeno‑oestrogens and anti‑androgens in
offshore‑produced water discharges (Thomas et al.,
Figure 6.3
2009) and of poly‑aromatic oxygen and sulphur
heterocyclic compounds causing dioxin‑like effects
in sediments (Brack and Schirmer, 2003).
Confirmation of compounds identified in
environmental samples as the likely cause of adverse
effects on aquatic organisms and communities
may be provided through the use of cause‑effect
chains (Figure 6.3). In Modelkey, a range of tools
has been compiled, advanced and tested for this
purpose in case studies (Hein et al., 2010). These
notably include in vitro assays on new toxicological
endpoints such as endocrine disruption of the
thyroid hormone transport protein transthyretin
(Weiss et al., 2009b), biomimetic tools for
bioavailability assessment (Sormunen et al.,
2010), in vivo biomarkers (Wenger et al., 2010),
and pollution-induced community tolerance
(PICT) approaches (McClellan et al., 2008). Whole
exposure‑effect chains have been established for
example for endocrine disrupters. These range
from in vitro effects, in vivo effects on snails in the
lab and in situ caging experiments to changes in the
community (Schmitt et al., 2010a, 2010b and 2011).
Exposure effect chain to confirm chemical contamination as a cause of
deteriorated ecological status
Ecology
Tools
Community
Community indices, PICT
Field
Population
Toxicology
Individual effect
Internal response
Population indices
In vivo bioassays
Chemistry
Internal concentration
Bioavailability
Biota
(tissue)
Chemical analysis
Biomimetic extracts
In vitro assays
External concentration
Sediment
water
In vivo biomarkers
In vitro assays
Chemical analysis
Source: Modelkey.
46
Matrix
Sediment
water
Conclusions
7Conclusions
7.1 Hazardous substances in water
affect aquatic life and pose risks to
human health
7.3 The potential risks posed
by emerging pollutants are
insufficiently understood
Many studies have documented a range of
detrimental impacts of hazardous substances
upon freshwater and marine biota. These effects
manifest themselves at molecular, cellular, tissue,
organ and ecosystem level. Such impacts diminish
the services provided by aquatic ecosystems, and
consequently the benefits, and notably the revenue,
which can be derived from them. Human exposure
to hazardous substances can occur via water,
through the consumption of contaminated fish and
shellfish and through the ingestion of contaminated
drinking water. The exceedance of regulatory levels
in seafood is documented for several hazardous
substances in Europe's seas.
The known persistence, bioaccumulation and toxicity
of a number of hazardous substances mean that
they are addressed by various pieces of European
legislation, notably through classification as a PS
or PHS under the EQSD. However, for a range of
emerging pollutants, the awareness of potential
effects has developed only recently and remains
incomplete. These emerging pollutants include
substances that have existed for some time, such
as pharmaceutical products and personal care
products, but also relatively new substances, such as
nanomaterials.
7.2 Legislation continues to play an
important role, but challenges
exist
A wide range of legislation has been implemented
to address the chemical quality of Europe's fresh
and marine waters, both directly and indirectly.
Collectively, this legislation encompasses a wide
range of measures and approaches.
Established legislation has produced clear positive
outcomes. Abatement measures introduced by
the IPPC Directive, for example, have led to
reduced metal emissions, and legislation relating
to the production, use and disposal of PCBs has
resulted in declines in concentrations found in
marine biota. A similar outcome has resulted from
the banning of TBT in anti‑fouling paints due
to its endocrine‑disrupting impacts on marine
invertebrates, although high levels in marine
sediments can still be observed in certain locations.
The implementation of more recent legislation,
such as REACH, the EQSD and the Pesticides
Framework Directive, is likely to play a key role
in strengthening the protection of both human
health and aquatic environments. However, despite
the comprehensive suite of legislation adopted in
Europe, some important challenges remain. These
are briefly highlighted in the following subsections.
Information regarding emerging pollutants is
relatively scarce, both regarding their concentrations
and their effects in the aquatic environment — an
observation which reflects the fact that emerging
pollutants are not, typically, included in routine
monitoring programmes. This gap creates a
conundrum. Unless a substance is regulated,
widespread monitoring is unlikely to be undertaken.
However, without such monitoring data, the risks to
the aquatic environment and to human health cannot
be robustly assessed, limiting the justification for
regulation, particularly given the expense associated
with monitoring and analysis. More information
is needed, therefore, with respect to emerging
pollutants, to build on the data provided by existing
initiatives such as the JRC monitoring programme
and the Norman network, to better identify those that
pose significant risk to environmental and human
health. Research studies must continue to play an
important role in this respect. However, these do not
necessarily provide Europe‑wide information at a
sufficient temporal and spatial scale. To support the
identification of substances for prioritisation under
the EQSD, a targeted EU‑wide approach is therefore
also desirable.
7.4 The ubiquity of some hazardous
substances presents particular
challenges
Certain hazardous substances, including mercury,
TBT and PAHs, can be described as persistent,
bioaccumulative and toxic, occur widely in
47
Conclusions
the environment, and have well documented
detrimental effects upon both environmental
and human health. Typically, their danger has
been known for some time and has led to the
implementation of strong regulation, with reduced
emissions to air and water being recorded. However,
their persistence and ubiquity, particularly in
sediment and biota, mean that they continue to
pose a risk to aquatic environments and that natural
recovery may take decades (e.g. with respect to
TBT in coastal sediment and biota). As a result of
long‑range transport in the atmosphere, some of
these substances have contaminated water bodies in
remote regions far from human activity (e.g. PAHs
in mountain lakes).
for some chemicals, the reporting of emissions to
water under E‑PRTR is incomplete. As a result, for
example, despite evidence of declining riverine
metal loads, it is not possible from reported data to
clearly track this trend back to reduced emissions
from industrial facilities. Achieving full reporting
under the PS inventory is of critical importance.
This should include comprehensive quantification
of emissions, enable each source to be apportioned,
establish a baseline against which trends over time
can be compared, and optimise the identification
of measures. European research studies such
as ScorePP and Socopse can support improved
quantification of emissions.
Overall, these various factors present a significant
challenge with respect to the regulation of such
substances under the WFD and the EQSD.
Remediation of highly contaminated hotspots may
be possible if technically and economically feasible,
but options are limited where strong legislation
is already in place. Moreover, such substances
are often hydrophobic and tend to accumulate in
sediment and biota. As a result, their concentrations
in these matrices are likely to be higher, and
therefore more detectable and measurable than
in water. This difference means that Member
States that apply a water column EQS for such
hydrophobic substances can underestimate their risk
to the aquatic environment. If different matrices are
used in different locations, the results may not be
comparable. Inconsistencies in the matrix used are
known to have led to unrepresentative differences
in the reporting of chemical status in the RBMPs of
different Member States.
7.6 Smart monitoring and assessment
tools are required
7.5 The quantitative understanding
of sources and emissions must be
improved
Information regarding the sources and emissions
of many hazardous substances remains
incomplete, limiting the scope to identify and
target appropriate measures. The EQSD requires
each Member State to establish an inventory of
emissions, discharges and losses for each river
basin district or part of a river basin district in its
territory. Inventories must cover both the diffuse
and the point source emissions of all PSs. Industrial
emissions will be a fundamental part of the
inventory and, as such, reporting under E‑PRTR
can represent an important component.
However, information provided in this report and
elsewhere (e.g. Greenpeace, 2010) suggests that,
48
It is not practical or affordable to sample and
analyse at sufficient spatial and temporal
resolution for hundreds of individual chemicals
within fresh and marine waters, including aquatic
biota and sediments. However, a focus upon a few
pre‑selected priority substances entails a strong
risk of missing other problematic substances.
Related to this aspect is the key issue of chemical
mixtures as found in the more polluted water
bodies of Europe. Laboratory studies have
shown that the combined effects of chemicals
upon aquatic life can be additive, meaning that
chemicals at concentrations which, individually,
would not lead to detectable adverse effects, can
result in observable detrimental effects when
combined. Recent European research has led to the
development of assessment tools that help to link
chemical contamination with observed deterioration
in ecological quality, establishing cause‑effect
relationships. Further development of such tools is
advisable and can be achieved through European
research programmes.
7.7 Chemicals should be produced and
used more sustainably
Despite the comprehensive suite of legislation
now implemented within Europe, the ubiquitous
use of chemicals in society represents a major
challenge with respect to the protection of aquatic
ecosystems; emissions of hazardous substances to
the environment, including fresh and marine waters,
can occur at all stages of their life cycle. Whilst these
emissions arise from various sources, the private
and public consumption of consumer goods is a
fundamental driver of the production and, therefore,
Conclusions
of the release of hazardous substances to the
environment.
The promotion of more sustainable chemical
consumption patterns for the future may be
achieved most effectively through a mix of policy
responses involving regulation, economic incentives
and information‑based instruments, including
awareness‑raising campaigns (EEA, 2010d).
Implementing a more sustainable approach to the
consumption and production of chemicals would
not only benefit Europe's environment but also
reduce the detrimental effects arising in other parts
of the world as a result of the growing proportion of
goods imported to Europe.
To help achieve a more sustainable production
of chemicals, wider implementation of 'green
chemistry' is required. This approach involves the
development of new processes and technologies
that maintain the quality of a product but reduce
or eliminate the use and generation of hazardous
substances. The adoption of sustainable, green
chemistry techniques has been shown to generate
financial benefits and hence provide competitive
advantage. Currently, however, there is no
comprehensive EU legislation on sustainable
chemistry in place (EEA, 2010b).
7.8 Climate change will also affect
chemical water quality
In the absence of appropriately strong measures,
climate change is likely to adversely impact chemical
water quality in a number of ways over the coming
decades. Hotter, drier summers and increasingly
severe and frequent droughts, for example, will
deplete river flows, reducing contaminant dilution
capacity and lead to elevated concentrations of
hazardous substances. In regions where more
intense rainfall is expected, the frequency and
severity of polluted urban stormflows is predicted
to increase (Nie et al., 2009; Waters et al., 2003),
whilst the re‑mobilisation and redistribution of
contaminated sediments will become more likely
(Hilscherova et al., 2007), for example as a result of
floods.
More frequent intense rainfall is also likely to
exacerbate the flushing of agricultural pollutants,
including pesticides and veterinary medicines,
to water bodies (Bloomfield et al., 2006; Boxall
et al., 2009). Moreover, an increased prevalence
of pests, weeds and diseases may lead to wider
and more frequent application of both pesticides
and veterinary medicines (Bloomfield et al., 2006;
Boxall et al., 2009), although higher temperatures
will increase the volatilisation of pesticides and
the degradation of pesticide residues in soil and
surface waters (Bloomfield et al., 2006). In the long
term, land‑use change driven by changes in climate
may have a more significant effect on pesticides in
the environment than the direct impacts of climate
change on specific pesticide fate and transport
processes (Bloomfield et al., 2006).
Ocean acidification, driven by increasing
atmospheric CO2, may change the speciation of
metals in seawater and, therefore, their interaction
with marine organisms (Millero et al., 2009). Coastal
erosion, likely to be exacerbated under climate
change, has led to the exposure of landfill sites in
Europe, with a clear potential for contamination of
coastal waters.
7.9 Training for expertise in
environmental risk assessment
should be supported
Investment in training is critical to ensure the
ongoing availability of skilled professionals to
undertake the environmental risk assessment of
hazardous substances such as those presented in
this report. One example with respect to human
health risk assessment is the 'European toxicology
risk assessment training' (TRISK) initiative, which
contributes directly to the training of risk assessors
across Member States, thus addressing the need
for human health risk assessment capability at
EU, national, and private sector levels over the
longer term. A similar initiative with respect to
environmental risk assessment could help to ensure
greater capability across the EU in the context
of assessing risks from hazardous substances in
Europe's aquatic environments.
49
Main abbreviations and acronyms
Main abbreviations and acronyms
50
CSO
Combined sewer overflow
EDA
Effect-directed analysis
E-PRTR
European Pollutant Release and Transfer Register
EQS
Environmental quality standard
EQSD
Environmental Quality Standards Directive
GWB
Groundwater body
GWD
Groundwater Directive
HELCOM
Helsinki Commission (the governing body of the Convention on the Protection of
the Marine Environment of the Baltic Sea Area, also called Helsinki Convention)
IPPC
Integrated Pollution Prevention and Control (Directive)
l
Litre
µg
Microgram
ng
Nanogram
OSPAR
Convention for the Protection of the Marine Environment of the North-East
Atlantic (opened for signature at the ministerial meeting of the Oslo and Paris
Commissions in Paris on 22 September 1992)
PAH
Polyaromatic hydrocarbon
PBT
Persistent, bioaccumulative and toxic (chemical)
PCB
Polychlorinated biphenyl
PHS
Priority hazardous substance
POP
Persistent organic pollutant
PS
Priority substance
RBD
River basin district
RBMP
River basin management plan
REACH
(Regulation on the) Registration, Evaluation, Authorisation and Restriction of
Chemicals
t
Tonne
TBT
Tributyltin
WFD
Water Framework Directive
WWTP
Wastewater treatment plant
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60
Annex 1
Annex 1 EU projects
With respect to hazardous substances, this report
refers to several key EU projects. These are:
•
'Functional tools for pesticide risk assessment
and management' (Footprint)
http://www.eu-footprint.org
•
'Models for assessing and forecasting the impact
of environmental key pollutants on marine
and freshwater ecosystems and biodiversity'
(Modelkey)
http://www.modelkey.org
•
'Network of reference laboratories for
monitoring of emerging environmental
pollutants' (Norman)
http://www.norman-network.net/ index_php.
php?menu2=public/about_us/about_
us&module=public/about_us/home
•
'Novel methods for integrated risk assessment of
cumulative stressors in Europe' (NoMiracle)
http://nomiracle.jrc.ec.europa.eu/default.aspx
•
'Source control of priority substances in Europe'
(Socopse)
http://www.socopse.se
•
'Source control options for reducing emissions
of priority pollutants' (ScorePP)
http://www.scorepp.eu
•
The 'European toxicology risk assessment
training' (TRISK) initiative
http://www.trisk-project.eu
61
Hazardous substances in Europe's fresh and
marine waters
An overview
2011 — 61 pp. — 21 x 29.7 cm
ISBN 978-92-9213-214-9
ISSN 1725-2237
doi:10.2800/78305
TH-AK-11-008-EN-N
doi:10.2800/78305
Kongens Nytorv 6
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Denmark
Tel.: +45 33 36 71 00
Fax: +45 33 36 71 99
Web: eea.europa.eu
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Hazardous substances in Europe`s fresh and marine waters — An

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